药学学报

Position	1		2
1	111.5			154.0
2	154.5		113.6	6.66, dd (8.0, 1.2)
3	99.9	6.98, s	126.7	7.00, dd (8.0, 8.0)
4	160.5		120.9	7.72, dd (8.0, 1.2)
4a	116.7		135.5
4b	126.2		116.8
5	110.2	9.21, s	159.8
6	148.9		99.2	6.42, d (2.2)
7	146.0		158.2
8	112.4	7.10, s	108.3	6.35, d (2.2)
8a	128.5		143.0
9	127.9	7.28, d (9.2)	31.4	2.72, dd (8.6, 5.0)
10	123.8	6.91, d (9.2)	22.0	2.62, dd (8.6, 5.0)
10a	135.8		125.1
1′	111.1
2′	154.4
3′	99.7	6.95, s
4′	160.6
4′a	116.5
4′b	126.5
5′	113.9	9.12, s
6′	145.3
7′	146.5
8′	112.5	7.08, s
8′a	128.1
9′	128.2	7.25, d (9.2)
10′	123.0	6.85, d (9.2)
10′a	135.8
4-OCH₃	56.3	4.18, s
5-OCH₃			55.8	3.80, s
6-OCH₃	56.1	4.05, s
4′-OCH₃	56.0	4.18, s

Position	1		2
1	111.5			154.0
2	154.5		113.6	6.66, dd (8.0, 1.2)
3	99.9	6.98, s	126.7	7.00, dd (8.0, 8.0)
4	160.5		120.9	7.72, dd (8.0, 1.2)
4a	116.7		135.5
4b	126.2		116.8
5	110.2	9.21, s	159.8
6	148.9		99.2	6.42, d (2.2)
7	146.0		158.2
8	112.4	7.10, s	108.3	6.35, d (2.2)
8a	128.5		143.0
9	127.9	7.28, d (9.2)	31.4	2.72, dd (8.6, 5.0)
10	123.8	6.91, d (9.2)	22.0	2.62, dd (8.6, 5.0)
10a	135.8		125.1
1′	111.1
2′	154.4
3′	99.7	6.95, s
4′	160.6
4′a	116.5
4′b	126.5
5′	113.9	9.12, s
6′	145.3
7′	146.5
8′	112.5	7.08, s
8′a	128.1
9′	128.2	7.25, d (9.2)
10′	123.0	6.85, d (9.2)
10′a	135.8
4-OCH₃	56.3	4.18, s
5-OCH₃			55.8	3.80, s
6-OCH₃	56.1	4.05, s
4′-OCH₃	56.0	4.18, s

Compound	IC₅₀/mg·mL^-1		Compound	IC₅₀/mg·mL^-1
2	0.15 ± 0.09		12	6.95 ± 0.80
6	0.37 ± 0.40	13	4.91 ± 0.12
7	0.08 ± 0.03	14	9.90 ± 1.67
8	7.61 ± 0.26	15	12.47 ± 1.48
9	0.69 ± 0.04	16	11.71 ± 2.01
10	8.71 ± 0.54	17	8.89 ± 1.32
11	1.43 ± 0.42	Acarbose	0.002 8 ± 0.000 5

Compound	IC₅₀/mg·mL^-1		Compound	IC₅₀/mg·mL^-1
2	0.15 ± 0.09		12	6.95 ± 0.80
6	0.37 ± 0.40	13	4.91 ± 0.12
7	0.08 ± 0.03	14	9.90 ± 1.67
8	7.61 ± 0.26	15	12.47 ± 1.48
9	0.69 ± 0.04	16	11.71 ± 2.01
10	8.71 ± 0.54	17	8.89 ± 1.32
11	1.43 ± 0.42	Acarbose	0.002 8 ± 0.000 5

铁棍山药皮化学成分研究

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杨俊杰 ¹ , 刘永康 ⁴ , 朱亮 ¹ , 吴其国 ¹^,³ , 侴桂新 ¹^,^* , 许红涛 ¹^,²^,^*

药学学报 | 研究论文 2025,60(12): 3749-3757

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药学学报 |研究论文 2025 , 60 (12) : 3749 -3757

铁棍山药皮化学成分研究

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杨俊杰¹, 刘永康⁴, 朱亮¹, 吴其国¹^,³, 侴桂新¹^,^*, 许红涛¹^,²^,^*

作者信息

¹上海中医药大学中药研究所, 上海 201203

²上海市中医药国际标准化研究院, 上海 201203

³安庆医药高等专科学校药学院, 安徽皖西南特色中药资源创新应用重点实验室, 安徽安庆 246052

⁴河南焦作市温县农业科学研究所, 河南焦作 454850

通讯作者:

侴桂新, E-mail: chouguixinzyb@126.com

许红涛, E-mail: xht8710@163.com

作者简介:

作者贡献:

杨俊杰是本文第一作者, 负责化合物分离和文章初稿撰写; 刘永康收集样品及提取; 吴其国负责活性筛选; 朱亮对分离和结构鉴定提供了一定帮助; 侴桂新和许红涛为本文通讯作者, 负责结构鉴定、数据核实及论文修改。

Chemical constituents from Chinese Yam (Dioscorea opposita Thunb.) peel

Jun-jie YANG¹, Yong-kang LIU⁴, Liang ZHU¹, Qi-guo WU¹^,³, Gui-xin CHOU¹^,^*, Hong-tao XU¹^,²^,^*

Affiliations

¹Institute of Chinese Materia Medica, Shanghai University of Traditional Chinese Medicine, Shanghai 201203, China

²Shanghai Academy of International Standardization for Traditional Chinese Medicine, Shanghai 201203, China

³Department of Pharmacy, Anqing Medical College, Key Laboratory of Innovative Application of Characteristic Traditional Chinese Medicine Resources in Southwest Anhui Province, Anqing 246052, China

⁴Wenxian Agricultural Science Research Institute, Jiaozuo 454850, China

出版时间: 2025-12-12 doi: 10.16438/j.0513-4870.2025-0981

文章导航

摘要

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采用硅胶柱色谱、中压液相色谱、葡聚糖凝胶Sephadex LH-20柱色谱以及高压制备液相色谱等技术, 从铁棍山药皮醇提取物的二氯甲烷部位分离得到19个化合物。通过理化性质和波谱数据分析, 鉴定出以下结构, 菲类(6个): 7′-hydroxybleformin E (1), 1,7-二羟基-5-甲氧基-9,10-二氢菲(2), 6-methoxycoelonin (3), 6-羟基-2,4,7-三甲氧基菲(4), 2,7-二羟基-4,6-二甲氧基菲(5), 5,7-二甲氧基-2,3-菲二醇(6); 联苄类(3个): 二氢松脂素(7), 2′,3-二羟基-5-甲氧基联苯(8), 去甲基山药素Ⅳ (9); 二苯基庚烷类(8个): 1,7-双(4-羟基苯基)-1,5-环氧-3-羟基庚烷(10), engelheptanoxide C (11), diosniponol A (12), (+)-hannokinol (13), (3S,5S)-3,5-二羟基-1-(4-羟基苯基)-7-(4-羟基-3-甲氧基苯基)庚烷(14), (3S,5S)-3,5-二羟基-1,7-双(4-羟基-3-甲氧基苯基)庚烷(15), 六氢姜黄素(16), (5S)-5-羟基-1-(4-羟基-3-甲氧基苯基)-7-(4-羟基苯基)-3-庚酮(17); 其他类(2个): 1个生物碱类, 阿魏酰酪胺(18)和1个脂肪酸类, 十八碳二烯酸-2,3-二羟丙基酯(19)。化合物1为新化合物; 首次对2的¹H NMR、¹³C NMR谱信号进行了全归属; 化合物 2、11、16~19为首次从薯蓣科植物中分离得到; 化合物3、6和12为首次从山药中分离得到。α-葡萄糖苷酶抑制活性筛选显示其中13个化合物对α-葡萄糖苷酶具有不同程度的抑制活性。

关键词

铁棍山药皮 / 化学成分 / 联苄 / 二苯基庚烷 / α-葡萄糖苷酶抑制活性

Abstract

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Nineteen compounds were isolated from the dichloromethane portion of the ethanol extract of Chinese Yam (Dioscorea opposita Thunb.) peel, using various chromatographic techniques including: silica gel column chromatography, medium-pressure liquid chromatography, Sephadex LH-20 gel column chromatography, and preparative high-performance liquid chromatography. Based on the physicochemical properties and spectral data, their structures were determined as follows: six phenanthrenes: 7′-hydroxybleformin E (1), 1,7-dihydroxy-5-methoxy-9,10-dihydrophenanthrene (2), 6-methoxycoelonin (3), 6-hydroxy-2,4,7-trimethoxyphenanthrene (4), 2,7-dihydroxy-4,6-dimethoxyphenanthrene (5), 5,7-dimethoxy-2,3-phenanthrenediol (6); three bibenzyls: dihydropinosylvin (7), 2′,3-dihydroxy-5-methoxybibenzyl (8), demethyl batatasin Ⅳ (9); eight diarylheptanoids: 1,7-bis(4-hydroxyphenyl)-1,5-epoxy-3-hydroxyheptane (10), engelheptanoxide C (11), diosniponol A (12), (+)-hannokinol (13), (3S,5S)-3,5-dihydroxy-1-(4-hydroxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)heptane (14), (3S,5S)-3,5-dihydroxy-1,7-bis(4-hydroxy-3-methoxyphenyl)heptane (15), hexahydrocurcumin (16), (5S)-5-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-7-(4-hydroxyphenyl)-3-heptanone (17); other compounds: one alkaloid, feruloyltyramine (18), and one fatty acid, octadecadienoic acid-2,3-dihydroxypropyl ester (19). Compound 1 is a new compound, whereas the ¹H NMR and ¹³C NMR spectral signals of 2 were fully attributed. compounds 2, 11, 16-19 were isolated from the Dioscoreaceae family for the first time, while compounds 3, 6, and 12 were the first to be reported from D. opposita. Among these, thirteen compounds showed differential inhibitory activities against α-glucosidase.

Key words

Chinese Yam (Dioscorea opposita Thunb.) peel / chemical composition / bibenzyls / diphenylheptane / α-glucosidase inhibitory activity

引用本文

杨俊杰, 刘永康, 朱亮, 吴其国, 侴桂新, 许红涛. 铁棍山药皮化学成分研究. 药学学报, 2025 , 60 (12) : 3749 -3757 . DOI: 10.16438/j.0513-4870.2025-0981

Jun-jie YANG, Yong-kang LIU, Liang ZHU, Qi-guo WU, Gui-xin CHOU, Hong-tao XU. Chemical constituents from Chinese Yam (Dioscorea opposita Thunb.) peel[J]. Acta Pharmaceutica Sinica, 2025 , 60 (12) : 3749 -3757 . DOI: 10.16438/j.0513-4870.2025-0981

正文

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山药为薯蓣科植物薯蓣(Dioscorea opposita Thunb.)的干燥根茎, 是主产于河南省焦作市温县、武陟等沿沁河一带(古怀庆府)的道地药材, 素有“四大怀药”之美誉^[1]。《神农本草经》记载其有“主治伤中, 补虚赢, 除寒热邪气, 补中益气力, 久服耳目聪明, 轻身不饥延年”等功效, 是我国传统的药食同源之佳品^[2]。在食用和加工过程中, 通常需要去除约占鲜品质量20%的山药皮, 这些副产物大多被直接废弃, 既造成资源浪费又带来环境负担^[3]。随着中药现代化的发展, 加强解决怀山药非药用部位的综合开发利用, 提升其资源价值已成为亟待解决的重要课题。本研究以温县铁棍山药皮为研究对象, 从其95%乙醇提取物的二氯甲烷萃取部位中, 系统分离鉴定了19个化合物(图1), 其中化合物1为新化合物, 化合物2、11、16~19为首次从薯蓣科植物中分离得到, 化合物3、6和12为首次从山药中分离得到。α-葡萄糖苷酶抑制活性筛选结果显示, 其中13个化合物表现出不同程度的抑制活性(IC₅₀值为0.08~12.47 mg·mL^-1), 为解决怀山药皮的综合开发利用提供了参考。

结果与讨论

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1　结构鉴定

化合物1为棕色粉末。根据其高分辨质谱(HR-ESI-MS)的准分子离子峰(m/z 525.153 4, 计算值525.154 4)推断其分子式为C₃₁H₂₄O₈, 不饱和度为20。化合物1的核磁数据表明其为联菲类化合物^[4], ¹H NMR (CD₃OD, 400 MHz)谱(表1)显示10个芳香氢质子信号, 包括6个单峰信号δ_H 9.21 (1H, s, H-5), 9.12 (1H, s, H-5′), 7.10 (1H, s, H-8), 7.08 (1H, s, H-8′), 6.98 (1H, s, H-3)和6.95 (1H, s, H-3′); 2对邻位耦合的双峰信号(J = 9.2 Hz): δ_H 7.28 (H-9)/6.91 (H-10), 7.25 (H-9′)/6.85 (H-10′)。此外, 还可观察到3个甲氧基信号δ_H 4.18 (6H, s, 4, 4′-OCH₃), 4.05 (3H, s, 6-OCH₃)。其¹³C NMR (CD₃OD, 100 MHz)谱(表1)共示有31个碳信号, 其中28个为芳烃碳, 包括8个连氧碳: δ_C 160.5/160.6 (C-4/4′), 154.5/154.4 (C-2/2′), 148.9/145.3 (C-6/6′), 146.0/146.5 (C-7/7′); 10个季碳: δ_C 135.8/135.8 (C-10a/10′a), 128.5/128.1 (C-8a/8′a), 126.2/126.5 (C-4b/4′b), 116.7/116.5 (C-4a/4′a), 111.5/111.1 (C-1/1′); 10个叔碳: δ_C 127.9/128.2 (C-9/9′), 123.8/123.0 (C-10/10′), 112.4/112.5 (C-8/8′), 110.2/113.9 (C-5/5′), 99.9/99.7 (C-3/3′), 以及3个甲氧基碳δ_C 56.3 (4-OCH₃), 56.1 (6-OCH₃), 56.0 (4′-OCH₃)。在化合物1的HMBC谱中, H-3与C-1/C-2/C-4/C-4a、H-5与C-4a/C-4b/C-6/C-7/C-8a、H-8与C-4b/C-6/C-7/C-9、H-9与C-4b/C-8/C-8a/C-10a、H-10与C-1/C-4a/C-8a/C-10a相关, 以及4-OCH₃和6-OCH₃分别与C-4和C-6的相关信号, 由此确定该菲类单元为2,7-二羟基-4,6-二甲氧基-菲。该单元结构通过¹H-¹H COSY谱(H-9/H-10相关)和NOESY谱(4-OCH₃/H-3、6-OCH₃/H-5相关)得到进一步确证(图2)。同样, 基于HMBC、¹H-¹H COSY和NOESY谱图数据的综合分析, 鉴定出另一个菲类化合物单元为2′,6′,7′-三羟基-4′-甲氧基菲(图2)。C-1和C-1′的化学位移值(δ_C 111.5和δ_C 118.1)及其季碳特征表明, 两个菲单元通过C-1与C-1′之间的C-C单键直接相连^[5]。综上, 化合物1被鉴定为2,7,2′,6′,7′-五羟基-4,6,4′-三甲氧基-1,1′-联菲, 其与bleformin E^[6]的区别仅在于7′位由羟基取代了甲氧基。故命名化合物1为7′-hydroxybleformin E。

化合物2为棕色粉末。根据其高分辨质谱(HR-ESI-MS)的准分子离子峰(m/z 243.102 3 [M+H]⁺, 计算值243.101 6)推断其分子式为C₁₅H₁₄O₃, 不饱和度为9。¹H NMR (400 MHz, CD₃OD)谱给出一组1,2,3-三取代苯环信号: δ_H 7.72 (1H, dd, J = 8.0, 1.2 Hz), 7.00 (1H, dd, J = 8.0, 8.0 Hz), 6.66 (1H, dd, J = 8.0, 1.2 Hz), 显示典型的邻位和间位耦合特征组合的芳香族ABC自旋系统^[7]。另外, 可见2个间位耦合的芳香氢δ_H 6.42 (1H, d, J = 2.2 Hz), 6.35 (1H, d, J = 2.2 Hz), 1个甲氧基δ_H 3.80 (1H, s)和2个亚甲基δ_H 2.72 (2H, dd, J = 8.6, 5.0 Hz), 2.62 (2H, dd, J = 8.6, 5.0 Hz)。¹³C NMR (100 MHz, CD₃OD)显示了12个芳烃碳δ_C 159.8, 158.2, 154.0, 143.0, 135.5, 126.7, 125.1, 120.9, 116.8, 113.6, 108.3, 99.2; 1个甲氧基碳δ_C 55.8和2个亚甲基碳δ_C 31.4, 22.2, 综上表明化合物2为9,10-二氢菲类化合物。根据HMBC谱中的相关信号: H-2/C-1/C-4/C-10a, H-3/C-1/C-2/C-4/C-4a, H-4/C-2/C-4b/C-10a, H-6/C-5/C-7/C-8/C-4b, H-8/C-6/C-7/C-9/C-4b, H-9/C-8/C-8a/C-10/C-10a/C-4b, H-10/C-1/C-4a/C-8a/10a, 5-OCH₃/C-5 (图3)。鉴定化合物2的结构为1,7-二羟基-5-甲氧基-9,10-二氢菲(1,7-dihydroxy-5-methoxy-9,10-dihydrophenanthrene)。经SciFinder数据库文献检索, 发现该化合物是从兰科植物新疆火烧兰Epipactis palustris (L.) Crantz根茎中分离得到^[8]。该研究通过质谱([M]⁺, 242和[M-15])、¹H NMR谱中δ_H 2.60 (单峰, 四个质子)和δ_H 3.74 (甲氧基信号), 及乙酸酐法证明2个羟基的存在, 并通过¹³C NMR谱与已知化合物coelonin (2,7-二羟基-4-甲氧基-9,10-二氢菲)的文献^{[9, 10]}数据比对, 鉴定该化合物为1,7-二羟基-5-甲氧基-9,10-二氢菲。这种有限的质谱和氢谱数据, 及结合文献比对而推断出的结构, 缺乏直接证据支持(如芳香氢数据及碳谱数据缺失, 未经二维谱验证等), 导致该化合物的结构鉴定存在不确定性。为此, 本文通过综合分析¹H NMR、¹³C NMR、HSQC及HMBC谱图数据, 准确鉴定了化合物2的结构, 并完成了所有碳氢信号的系统归属。

2　活性评价

山药皮中部分化合物对α-葡萄糖苷酶的抑制活性筛选结果见表2, 阳性药阿卡波糖的IC₅₀为0.002 8 mg·mL^-1, 化合物2、6、7和9具有中等抑制活性IC₅₀分别为0.15、0.37、0.08和0.69 mg·mL^-1, 其他化合物活性较弱。

实验部分

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1D和2D NMR用Bruker AVANCE-Ⅲ (400 MHz)型核磁共振波谱仪测定(四甲基硅烷为内标, 化学位移δ用ppm表示, 德国Bruker公司)。中压液相色谱仪(MPLC, Grace, 美国); 多维制备色谱仪(Puri Master-7000, 上海科哲生化科技有限公司); 岛津高效液相色谱仪(岛津, 日本); 制备色谱柱(Shiseido Capcellpak C18, 250 mm × 20 mm); Sephadex LH-20 (25~100 μm, 通用电器医疗集团, 美国); YMC gel ODS-AQ (50 µm, YMC有限公司, 日本); MCI gel CHP20P (75~150 μm, 三菱化学有限公司, 日本); 柱层析硅胶(100~200目, 200~300目, 青岛海洋化工厂分厂); 薄层层析及制备型薄层层析HSGF254硅胶板(烟台江友硅胶开发有限公司); 高效液相色谱用乙腈、甲醇(Dikma, 色谱级, 美国); 薄层层析用乙酸乙酯、三氯甲烷、甲醇(分析纯, 国药集团); 柱层析用乙酸乙酯、二氯甲烷、甲醇(工业级, 上海润捷化学试剂有限公司)。温县铁棍山药皮由河南省温县怀药办提供, 并由温县怀药办刘永康老师鉴定为薯蓣科薯蓣Dioscorea opposita Thunb.的干燥根茎皮, 凭证标本(No.SYP 2021040201)保存于上海中医药大学中药研究所。

1　提取与分离

干燥温县铁棍山药皮8.20 kg, 粉碎, 用95%乙醇室温冷浸提取三次(3×70 L), 浓缩后得到浸膏1.0 kg。再用二氯甲烷将浸膏溶解后与2倍量的100~200目硅胶∶硅藻土(1∶1)拌样, 依次用石油醚、二氯甲烷、乙酸乙酯和甲醇萃取。

二氯甲烷部位33.8 g与1倍量的100~200目硅胶拌样后, 经硅胶(200~300目)柱色谱, 石油醚-乙酸乙酯(5∶1~0∶1)不同比例依次进行洗脱, TLC检测, 合并相同组分, 得到4个组分(Fr. 1~Fr. 4)。

Fr. 1共计2.31 g, 经混合溶剂石油醚-二氯甲烷-甲醇(5∶5∶1)溶解后上样甲醇凝胶柱洗脱。共获得4个组分(Fr. 1-1~Fr. 1-4)。Fr. 1-3共计1.1 g, 经制备液相色谱(35%乙腈-水等度洗脱), 得到化合物7 (50 mg, t_R = 45.0 min)和8 (632 mg, t_R = 50.0 min)。Fr. 1-4共计370.0 mg, 经甲醇重结晶得到化合物4 (200 mg)。

Fr. 2共计15.14 g与2倍量的ODS拌样后, 上样于中压制备柱, 经甲醇-水(3∶7~1∶0)梯度洗脱, 共获得10个组分(Fr. 2-1~Fr. 2-10)。Fr. 2-3共计1.6 g, 与1倍量的硅胶拌样后, 上样于20倍装柱量的硅胶柱, 经石油醚-乙酸乙酯(2∶1)等度洗脱后, 再经制备液相色谱(35%~60%乙腈-水梯度洗脱30 min), 得到化合物5 (10 mg, t_R = 12.2 min)、11 (10 mg, t_R = 7.1 min)、13 (23 mg, t_R = 6.1 min)、14 (20 mg, t_R = 6.4 min)和18 (30 mg, t_R = 12.5 min)。按同样的方法从Fr. 2-4 (500.0 mg)和Fr. 2-8 (390.0 mg)组分中获得化合物1 (30 mg, t_R = 14.5 min)、12 (35 mg, t_R = 7.6 min)、15 (45 mg, t_R = 6.6 min)、16 (110 mg, t_R = 8.8 min)和17 (45 mg, t_R = 8.5 min)。

Fr. 3共计6.3 g与1倍量的ODS拌样后, 上样于中压制备柱, 经甲醇-水(3∶7~1∶0)梯度洗脱, 共获得4个组分(Fr. 3-1~Fr. 3-4)。Fr. 3-2共计100 mg, 经制备液相色谱(35%乙腈-水等度洗脱)得到化合物3 (10 mg, t_R = 18.0 min)和2 (30 mg, t_R = 20.0 min)。Fr. 3-4共计700.0 mg, 经甲醇重结晶得到化合物6 (400 mg)。Fr. 3-5共计100 mg, 经制备液相色谱梯度洗脱, 乙腈-水(35∶65~95∶5), 得到化合物19 (10 mg, t_R = 32.0 min)。

Fr. 4共计1.84 g经混合溶剂石油醚-二氯甲烷-甲醇(5∶5∶1)溶解后上样甲醇凝胶柱洗脱。共获得4个组分(Fr. 4-1~Fr. 4-4)。Fr. 4-3共计200 mg, 经制备液相色谱(35%~60%乙腈-水梯度洗脱30 min), 得到化合物9 (45 mg, t_R = 8.8 min)和10 (50 mg, t_R = 6.8 min)。

2　结构鉴定

7′-Hydroxybleformin E (1)为棕色粉末。HR-ESI-MS m/z: 525.153 4 [M+H]⁺ (计算值C₃₁H₂₅O₈⁺, 525.154 4); IR (KBr): 3 297、2 936、2 848、1 731、1 585、1 463、1 445、1 201、1 135 cm^-1; ¹ H NMR和¹³C NMR数据见表1。

1,7-Dihydroxy-5-methoxy-9,10-dihydrophenanthrene (2)为棕色粉末。HR-ESI-MS m/z 243.102 3 [M+H]⁺, (计算值C₁₅H₁₅O₃⁺, 243.101 6); IR (KBr): 3 261、2 980、2 839、2 434、1 593、1 452、1 325、1 310、1 157、1 064、796 cm^-1; ¹H NMR和¹³C NMR数据见表1。

6-Methoxycoelonin (3)为棕色粉末。HR-ESI-MS m/z: 273.111 4 [M+H]⁺ (计算值C₁₆H₁₇O₄⁺, 273.112 1); ¹H NMR (400 MHz, CD₃OD) δ_H: 7.84 (1H, s, H-4), 6.63 (1H, s, H-1), 6.41 (1H, d, J = 2.3 Hz, H-6), 6.31 (1H, d, J = 2.3 Hz, H-8), 3.85 (6H, s, 4,6-OCH₃), 2.65 (4H, m, H-9, 10); ¹³C NMR (100 MHz, CD₃OD) δ_C: 159.0 (C-5), 157.6 (C-7), 146.6 (C-3), 145.2 (C-2), 141.9 (C-8a), 132.2 (C-10a), 126.1 (C-4a), 116.8 (C-4b), 115.3 (C-1), 113.6 (C-4), 108.5 (C-8), 99.4 (C-6), 56.6 (3-OCH₃), 56.0 (5-OCH₃), 32.0 (C-9), 30.2 (C-10)。波谱数据与文献报道的6-methoxycoelonin^[11]一致, 故该化合物确定为6-methoxycoelonin。

6-Hydroxy-2,4,7-trimethoxyphenanthrene (4)为棕色粉末。HR-ESI-MS m/z: 285.113 3 [M+H]⁺ (计算值C₁₇H₁₇O₄⁺, 285.112 1); ¹H NMR (400 MHz, CDCl₃) δ_H: 9.12 (1H, s, H-5), 7.60 (1H, d, J = 8.7 Hz, H-9), 7.50 (1H, d, J = 8.8 Hz, H-10), 7.18 (1H, s, H-8), 6.86 (1H, d, J = 2.5 Hz, H-1), 6.73 (1H, d, J = 2.5 Hz, H-3), 4.07 (3H, s, 7-OCH₃), 4.00 (3H, s, 4-OCH₃), 3.94 (3H, s, 2-OCH₃); ¹³C NMR (100 MHz, CDCl₃) δ_C: 159.6 (C-2), 157.6 (C-4), 145.5 (C-7), 145.1 (C-6), 134.8 (C-10a), 127.6 (C-4b), 126.9 (C-8a), 125.7 (C-9), 124.9 (C-10), 115.5 (C-4a), 112.2 (C-5), 107.6 (C-1), 101.1 (C-8), 98.9 (C-3), 55.8 (7-OCH₃), 55.6 (4-OCH₃), 55.4 (2-OCH₃)。波谱数据与文献报道的6-hydroxy-2,4,7-trimethoxyphenanthrene^[12]一致, 故该化合物确定为6-hydroxy-2,4,7-trimethoxyphenanthrene。

2,7-Dihydroxy-4,6-dimethoxyphenanthrene (5)为深棕色粉末。HR-ESI-MS m/z: 271.096 6 [M+H]⁺ (计算值C₁₆H₁₅O₄⁺, 271.096 5); ¹H NMR (400 MHz, CD₃OD) δ_H: 8.97 (1H, s, H-5), 7.53 (1H, d, J = 8.7 Hz, H-9), 7.35 (1H, d, J = 8.8 Hz, H-10), 7.24 (1H, d, J = 5.6 Hz, H-8), 6.79 (1H, d, J = 2.4 Hz, H-1), 6.71 (1H, d, J = 2.3 Hz, H-3), 4.06 (3H, s, 4-OCH₃), 3.96 (3H, s, 6-OCH₃); ¹³C NMR (100 MHz, CD₃OD) δ_C: 160.9 (C-4), 157.4 (C-2), 147.8 (C-6), 146.9 (C-7), 136.5 (C-10a), 128.5 (C-8a), 127.9 (C-9), 126.9 (C-4b), 125.1 (C-10), 115.5 (C-4a), 113.7 (C-8), 109.4 (C-5), 105.4 (C-1), 99.8 (C-3), 56.1 (6-OCH₃), 55.9 (4-OCH₃)。波谱数据与文献报道的2,7-dihydroxy-4,6-dimethoxyphenanthrene^[13]一致, 故该化合物确定为2,7-dihydroxy-4,6-dimethoxyphenanthrene。

5,7-Dimethoxy-2,3-phenanthrenediol (6)为深棕色粉末。HR-ESI-MS m/z: 271.096 7 [M+H]⁺ (计算值C₁₆H₁₅O₄⁺, 271.096 5); ¹H NMR (400 MHz, CD₃OD) δ_H: 8.99 (1H, s, H-4), 7.47 (1H, d, J = 8.7 Hz, H-9), 7.39 (1H, d, J = 8.8 Hz, H-10), 7.16 (1H, s, H-1), 6.85 (1H, d, J = 2.5 Hz, H-8), 6.71 (1H, d, J = 2.5 Hz, H-6), 4.04 (3H, s, 4-OCH₃), 3.87 (3H, s, 6-OCH₃); ¹³C NMR (100 MHz, CD₃OD) δ_C: 160.6 (C-5), 158.7 (C-7), 146.6 (C-2), 145.5 (C-3), 136.0 (C-8a), 128.4 (C-10a), 128.3 (C-10), 126.1 (C-9), 125.3 (C-4a), 116.6 (C-4), 113.7 (C-1), 112.7 (C-4b), 102.3 (C-8), 99.6 (C-6), 55.9 (7-OCH₃), 55.7 (5-OCH₃)。波谱数据与文献报道的5,7-dimethoxy-2,3-phenanthrenediol^[14]一致, 故该化合物确定为5,7-dimethoxy-2,3-phenanthrenediol。

Dihydropinosylvin (7)为棕色粉末。HR-ESI-MS m/z: 215.106 5 [M+H]⁺ (计算值C₁₄H₁₅O₂⁺, 215.106 7); ¹H NMR (400 MHz, CD₃OD) δ_H: 7.24 (2H, m, H-3′, 5′), 7.14 (3H, m, H-2′, 4′, 6′), 6.14 (2H, s, H-2, 6), 6.09 (1H, s, H-4) 2.85 (2H, m, H-a), 2.72 (2H, m, H-a′); ¹³C NMR (100 MHz, CD₃OD) δ_C: 159.4 (C-3, 5), 145.4 (C-1), 143.2 (C-1′), 129.5 (C-2′, 6′), 129.3 (C-3′, 5′), 126.8 (C-4′), 108.0 (C-2, 6), 101.2 (C-4), 39.3 (C-a), 38.9 (C-a′)。波谱数据与文献报道的dihydropinosylvin^[15]一致, 故该化合物确定为dihydropinosylvin。

2′,3-Dihydroxy-5-methoxybibenzyl (8)为棕色粉末。HR-ESI-MS m/z: 245.118 0 [M+H]⁺ (计算值C₁₅H₁₇O₃⁺, 245.117 2); ¹H NMR (400 MHz, CD₃OD) δ_H: 6.99 (2H, m, H-4′, 6′), 6.75 (1H, dd, J = 8.4, 0.9 Hz, H-3′), 6.70 (1H, td, J = 7.4, 1.1 Hz, H-5′), 6.28 (1H, s, H-2), 6.25 (1H, s, H-6), 6.18 (1H, t, J = 2.2 Hz, H-4), 3.69 (3H, s, 5-OCH₃), 2.83 (2H, m, H-a), 2.75 (2H, m, H-a′); ¹³C NMR (100 MHz, CD₃OD) δ_C: 162.1 (C-5), 159.2 (C-3), 156.3 (C-2′), 146.2 (C-1), 131.2 (C-6′), 129.4 (C-1′), 128.0 (C-4′), 120.4 (C-3′), 115.8 (C-5′), 109.1 (C-6), 106.5 (C-2), 99.8 (C-4), 55.5 (5-OCH₃), 37.4 (C-a), 33.6 (C-a′)。波谱数据与文献报道的2′,3-dihydroxy-5-methoxybibenzyl^[16]一致, 故该化合物确定为2′,3-dihydroxy-5-methoxybibenzyl。

Demethyl batatasin Ⅳ (9)为深棕色粉末。HR-ESI-MS m/z: 231.101 7 [M+H]⁺ (计算值C₁₄H₁₅O₃⁺, 231.101 6); ¹H NMR (400 MHz, CD₃OD) δ_H: 6.98 (2H, m, H-4′, 6′), 6.75 (1H, d, J = 7.7 Hz, H-3′), 6.71 (1H, td, J = 7.4, 1.1 Hz, H-5′), 6.20 (2H, d, J = 1.9 Hz, H-2, 6), 6.10 (1H, d, J = 1.7 Hz, H-4), 2.82 (2H, m, H-a), 2.70 (2H, m, H-a′); ¹³C NMR (100 MHz, CD₃OD) δ_C: 159.2 (C-3, 5), 156.2 (C-2′), 146.2 (C-1), 131.1 (C-6′), 129.5 (C-1′), 127.9 (C-4′), 120.5 (C-3′), 115.8 (C-5′), 108.1 (C-2, 6), 101.0 (C-4), 37.4 (C-a), 33.6 (C-a′)。波谱数据与文献报道的demethyl batatasin Ⅳ一致^[17], 故该化合物确定为demethyl batatasin Ⅳ。

1,7-bis(4-hydroxyphenyl)-1,5-epoxy-3-hydroxyheptane (10)为棕色粉末。HR-ESI-MS m/z: 315.159 3 [M+H]⁺ (计算值C₁₉H₂₃O₄⁺, 315.159 1); ¹H NMR (400 MHz, CD₃OD) δ_H: 7.20 (2H, d, J = 8.5 Hz, H-2′, 6′), 6.99 (2H, d, J = 8.4 Hz, H-3′,5′), 6.77 (1H, d, J = 8.2 Hz, H-2″, 6″), 6.68 (1H, dd, J = 8.4, 1.0 Hz, H-3″, 5″), 4.25 (1H, d, J = 11.4 Hz, H-1), 3.83 (1H, m, H-3), 3.44 (1H, s, H-5), 2.64 (2H, m, H-7), 2.07 (1H, m, H-2β), 1.95 (1H, m, H-4β), 1.85 (1H, td, J = 13.9, 8.2 Hz, H-6), 1.72 (1H, td, J = 12.6, 7.9 Hz, H-6), 1.43 (1H, dd, J = 23.5, 11.5 Hz, H-2α), 1.24 (1H, dd, J = 23.3, 11.3 Hz, H-4α); ¹³C NMR (100 MHz, CD₃OD) δ_C: 157.9 (C-4′), 156.3 (C-4″), 134.6 (C-1′), 134.2 (C-1″), 130.4 (C-2″, 6″), 128.6 (C-2′, 6′), 116.1 (C-3″, 5″), 116.0 (C-3′, 5′), 78.7 (C-1), 76.3 (C-5), 69.0 (C-3), 43.6 (C-2), 41.8 (C-4), 39.3 (C-6), 31.9 (C-7)。波谱数据与文献报道的1,7-bis(4-hydroxyphenyl)-1,5-epoxy-3-hydroxyheptane^{[18, 19]}一致, 故该化合物确定为1,7-bis(4-hydroxyphenyl)-1,5-epoxy-3-hydroxyheptane。

Engelheptanoxide C (11)为棕色粉末。HR-ESI-MS m/z: 345.169 8 [M+H]⁺ (计算值C₂₀H₂₅O₅⁺, 345.169 7); ¹H NMR (400 MHz, CD₃OD) δ_H: 7.00 (2H, d, J = 8.4 Hz, H-2″, 6″), 6.97 (1H, d, J = 1.5 Hz, H-2′), 6.77 (1H, dd, J = 8.1, 1.8 Hz, H-6′), 6.77 (1H, d, J = 8.1 Hz, H-5′), 6.68 (2H, d, J = 8.4 Hz, H-3″, 5″), 4.26 (1H, d, J = 11.3 Hz, H-1), 3.86 (3H, s, OCH₃-3′), 3.82 (1H, m, H-3), 3.44 (1H, m, H-5), 2.65 (2H, m, H-7), 2.09 (1H, m, H-2β), 1.96 (1H, m, H-4β), 1.86 (1H, dt, J = 13.8, 6.8 Hz, H-6), 1.74 (1H, ddd, J = 16.7, 8.8, 4.3 Hz, H-6), 1.43 (1H, m, H-2α), 1.24 (1H, m, H-4α); ¹³C NMR (100 MHz, CD₃OD) δ_C: 156.4 (C-4″), 148.2 (C-3′), 147.0 (C-4′), 135.3 (C-1″), 134.2 (C-1′), 130.4 (C-2″, 6″), 120.0 (C-6′), 116.1 (C-3″, 5″), 115.9 (C-5′), 111.1 (C-2′), 78.9 (C-1), 76.4 (C-5), 69.0 (C-3), 56.4 (OCH₃-3′), 43.7 (C-2), 41.8 (C-4), 39.2 (C-6), 31.8 (C-7)。波谱数据与文献报道的engelheptanoxide C^[20]一致, 故该化合物确定为engelheptanoxide C。

Diosniponol A (12)为深棕色粉末。HR-ESI-MS m/z: 375.179 9 [M+H]⁺ (计算值C₂₁H₂₇O₆⁺, 375.180 2); ¹H NMR (400 MHz, CD₃OD) δ_H: 6.96 (1H, d, J = 1.3 Hz, H-2′), 6.82 (1H, dd, J = 8.2, 1.5 Hz, H-6′), 6.77 (1H, d, J = 8.1 Hz, H-5′), 6.74 (1H, d, J = 1.5 Hz, H-2″), 6.70 (1H, d, J = 8.0 Hz, H-5″), 6.61 (1H, dd, J = 8.0, 1.6 Hz, H-6″), 4.24 (1H, d, J = 10.3 Hz, H-1), 3.85 (3H, s, OCH₃-3′), 3.82 (1H, m, H-3), 3.77 (3H, s, OCH₃-3″), 3.43 (1H, m, H-5), 2.65 (2H, m, H-7), 2.09 (1H, m, H-2β), 1.96 (1H, m, H-4β), 1.86 (1H, dt, J = 13.8, 6.8 Hz, H-6), 1.75 (1H, m, H-6), 1.43 (1H, dd, J = 23.4, 11.5 Hz, H-2α), 1.24 (1H, dd, J = 23.2, 11.4 Hz, H-4α); ¹³C NMR (100 MHz, CD₃OD) δ_C: 148.8 (C-3″), 148.8 (C-3′), 147.0 (C-4′), 145.4 (C-4″), 135.4 (C-1′), 135.0 (C-1″), 121.8 (C-6″), 120.0 (C-6′), 116.1 (C-5″), 115.9 (C-5′), 113.2 (C-2″), 111.1 (C-2′), 78.9 (C-1), 76.3 (C-5), 69.0 (C-3), 56.4 (OCH₃-3′), 56.3 (OCH₃-3″), 43.7 (C-2), 41.8 (C-4), 39.1 (C-6), 32.3 (C-7)。波谱数据与文献报道的diosniponol A^[21]一致, 故该化合物确定为diosniponol A。

(+)-Hannokinol (13)为棕色粉末。HR-ESI-MS m/z: 317.174 6 [M+H]⁺ (计算值C₁₉H₂₅O₄⁺, 317.174 7); ¹H NMR (400 MHz, CD₃OD) δ_H: 7.00 (4H, d, J = 8.5 Hz, H-2′, 6′, 2″, 6″), 6.69 (4H, dd, J = 8.2, 1.7 Hz, H-3′, 5′, 3″, 5″), 3.82 (2H, dd, J = 11.7, 5.8 Hz, H-3, 5), 2.66 (2H, m, H-1), 2.54 (2H, m, H-7), 1.68 (4H, m, H-2, 6), 1.54 (2H, t, J = 6.1 Hz, H-4); ¹³C NMR (100 MHz, CD₃OD) δ_C: 156.3 (C-4′, 4″), 134.5 (C-1′, 1″), 130.3 (C-2′, 2″), 116.1 (C-5′, 5″), 68.7 (C-1), 45.6 (C-5), 41.4 (C-3), 32.1 (C-7)。波谱数据与文献报道的(+)-hannokinol^[22]一致, 故该化合物确定为(+)-hannokinol。

(3S,5S)-3,5-Dihydroxy-1-(4-hydroxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)heptane (14)为棕黑色粉末。HR-ESI-MS m/z: 347.185 6 [M+H]⁺ (计算值C₂₀H₂₇O₅⁺, 347.185 3); ¹H NMR (400 MHz, CD₃OD) δ_H: 7.00 (2H, d, J = 8.4 Hz, H-2′, 6′), 6.76 (1H, brs, H-2″), 6.69 (3H, m, H-3′, 5′, 5″), 6.62 (1H, dd, J = 8.0, 1.8 Hz, H-6″), 3.82 (2H, m, H-3, 5), 3.81 (3H, s, OCH₃-3″), 2.67 (2H, m, H-1), 2.55 (2H, m, H-7), 1.69 (4H, m, H-2, 6), 1.54 (2H, t, J = 6.0 Hz, H-4); ¹³C NMR (100 MHz, CD₃OD) δ_C: 156.3 (C-4′), 148.8 (C-3″), 145.4 (C-4″), 135.3 (C-1″), 134.5 (C-1′), 130.3 (C-2′, 6′), 121.8 (C-6″), 116.1 (C-3′, 5′, 5″), 113.2 (C-2″), 68.7 (C-3, 5), 56.3 (OCH₃-3″), 45.6 (C-4), 41.4 (C-6), 41.3 (C-2), 32.6 (C-1), 32.1 (C-7)。波谱数据与文献报道的(3S,5S)-3,5-dihydroxy-1-(4-hydroxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)heptane^[23]一致, 故该化合物确定为(3S,5S)-3,5-dihydroxy-1-(4-hydroxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)heptane。

(3S,5S)-3,5-Hihydroxy-1,7-bis(4-hydroxy-3-methoxyphenyl)heptane (15)为棕色粉末。HR-ESI-MS m/z: 377.196 1 [M+H]⁺ (计算值C₂₁H₂₉O₆⁺, 377.195 9); ¹H NMR (400 MHz, CD₃OD) δ_H: 6.76 (2H, d, J = 1.5 Hz, H-2′, 2″), 6.69 (2H, d, J = 8.0 Hz, H-5′, 5″), 6.62 (2H, dd, J = 8.0, 1.5 Hz, H-6′, 6″), 3.82 (8H, m, H-3, 5, OCH₃-3′, 3″), 2.67 (2H, m, H-1β, H-7β), 2.56 (2H, m, H-1α, H-7α), 1.70 (4H, m, H-2, 6), 1.56 (2H, t, J = 6.0 Hz, H-4); ¹³C NMR (100 MHz, CD₃OD) δ_C: 148.8 (C-3′, 3″), 145.4 (C-4′, 4″), 135.2 (C-1′, 1″), 121.8 (C-6′, 6″), 116.1 (C-5′, 5″), 113.2 (C-2′, 2″), 68.7 (C-3, 5), 56.3 (OCH₃-3′, 3″), 45.7 (C-4), 41.4 (C-2, 6), 32.6 (C-1, 7)。波谱数据与文献报道的(3S,5S)-3,5-dihydroxy-1,7-bis(4-hydroxy-3-methoxyphenyl)heptane^[24]一致, 故该化合物确定为(3S,5S)-3,5-dihydroxy-1,7-bis(4-hydroxy-3-methoxyphenyl)heptane。

Hexahydrocurcumin (16)为棕色粉末。HR-ESI-MS m/z: 375.180 1 [M+H]⁺ (计算值C₂₁H₂₇O₆⁺, 375.180 2); ¹H NMR (400 MHz, CD₃OD) δ_H: 6.74 (2H, d, J = 2.3 Hz, H-2′, 2″), 6.70 (2H, d, J = 8.0 Hz, H-5′), 6.68 (2H, dd, J = 8.0, 1.5 Hz, H-5″), 6.60 (2H, dd, J = 7.9, 2.1 Hz, H-6′, 6″), 4.01 (1H, m, H-5), 3.81 (3H, s, OCH₃-3′), 3.79 (3H, s, OCH₃-3″), 2.79~2.46 (8H, m, H-1, 2, 4, 7), 1.68 (2H, m, H-6); ¹³C NMR (100 MHz, CD₃OD) δ_C: 211.9 (C-3), 148.8 (C-3′), 148.8 (C-3″), 145.7 (C-4′), 145.5 (C-4″), 134.8 (C-1″), 134.0 (C-1′), 121.8 (C-6″), 121.7 (C-6′), 116.1 (C-5′′), 116.1 (C-5′), 113.1 (C-2′), 113.0 (C-2″), 68.2 (C-5), 56.3 (OCH₃-3′, 3″), 51.2 (C-4), 46.3 (C-2), 40.4 (C-6), 32.4 (C-7), 30.2 (C-1)。波谱数据与文献报道的hexahydrocurcumin^[25]一致, 故该化合物确定为hexahydrocurcumin。

(5S)-5-Hydroxy-1-(4-hydroxy-3-methoxyphenyl)-7-(4-hydroxyphenyl)-3-heptanone (17)为棕色粉末。HR-ESI-MS m/z: 345.170 0 [M+H]⁺ (计算值C₂₀H₂₅O₅⁺, 345.169 7); ¹H NMR (400 MHz, CD₃OD) δ_H: 6.98 (2H, d, J = 8.3 Hz, H-2″, 6″), 6.75 (1H, d, J = 2.3 Hz, H-5′), 6.69 (3H, m, H-2′,3″, 5″), 6.60 (2H, m, H-6′), 4.02 (1H, m, H-5), 3.81 (3H, s, OCH₃-3′), 2.44~2.81 (8H, m, H-1, 2, 4, 7), 1.67 (2H, m, H-6); ¹³C NMR (100 MHz, CD₃OD) δ_C: 211.9 (C-3), 156.6 (C-4″), 148.8 (C-3′), 145.7 (C-4′), 134.9 (C-1″), 134.1 (C-1′), 130.3 (C-2″, 6″), 121.8 (C-6′), 116.1 (C-5′), 116.1 (C-3″, 5″), 113.1 (C-2′), 68.2 (C-5), 56.3 (OCH₃-3′), 51.2 (C-4), 46.3 (C-2), 40.4 (C-6), 32.4 (C-7), 30.2 (C-1)。波谱数据与文献报道的(5S)-5-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-7-(4-hydroxyphenyl)-3-heptanone^[26]一致, 故该化合物确定为(5S)-5-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-7-(4-hydroxyphenyl)-3-heptanone。

Feruloyltyramine (18)为深棕色粉末。HR-ESI-MS m/z: 314.139 8 [M+H]⁺ (计算值C₁₈H₂₀NO₄⁺, 314.138 7); ¹H NMR (400 MHz, CD₃OD) δ_H: 7.44 (2H, d, J = 15.7 Hz, H-7′), 7.09 (1H, s, H-2′), 7.04 (1H, d, J = 8.3 Hz, H-2, 6), 7.00 (1H, m, H-6′), 6.79 (1H, d, J = 8.1 Hz, H-5′), 6.72 (1H, d, J = 8.4 Hz, H-3, 5), 6.41 (1H, d, J = 15.7 Hz, H-8′), 3.85 (3H, s, OCH₃-3′), 3.46 (2H, t, J = 7.3 Hz, H-8), 2.74 (2H, t, J = 7.3 Hz, H-7); ¹³C NMR (100 MHz, CD₃OD) δ_C: 169.2 (C-9′), 156.8 (C-4), 149.7 (C-4′), 149.2 (C-3′), 142.0 (C-7′), 131.3 (C-1), 130.7 (C-2, 6), 128.2 (C-1′), 123.2 (C-6′), 118.7 (C-8′), 116.5 (C-5′), 116.3 (C-3, 5), 111.5 (C-2′), 56.4 (OCH₃-3′), 42.9 (C-8), 35.7 (C-7)。波谱数据与文献报道的feruloyltyramine^[27]一致, 故该化合物确定为feruloyltyramine。

Octadecadienoic acid-2,3-dihydroxypropyl ester (19)为棕色粉末。HR-ESI-MS m/z: 355.282 1 [M+H]⁺ (计算值C₂₁H₃₉O₄⁺, 355.284 3); ¹H NMR (400 MHz, CD₃OD) δ_H: 5.43~5.26 (4H, m, H-9′, 10′, 12′, 13′), 4.15 (1H, dd, J = 11.4, 4.4 Hz, H-1β), 4.06 (1H, dd, J = 11.4, 6.2 Hz, H-1α), 3.85~3.78 (1H, m, H-3α), 3.55 (1H, dd, J = 5.6, 1.6 Hz, H-3β), 2.78 (2H, t, J = 6.2 Hz, H-11′), 2.35 (2H, t, J = 7.4 Hz, H-2′), 2.07 (4H, q, J = 6.6 Hz, H-8′, 14′), 1.62 (2H, m, H-3′), 1.42~1.24 (14H, m, H-4′~7′, 15′~17′), 0.91 (3H, t, J = 6.9 Hz, 18′-CH₃); ¹³C NMR (100 MHz, CD₃OD) δ_C: 175.4 (C-1′), 130.9 (C-9′), 130.9 (C-13′), 129.1 (C-10′), 129.0 (C-12′), 71.1 (C-2), 66.5 (C-3), 64.1 (C-1), 34.9 (C-2′), 32.7 (C-7′), 30.7 (C-15′), 30.5 (C-6′), 30.3 (C-5′), 30.2 (C-4′), 30.2 (C-3′), 28.2 (C-8′, 14′), 26.5 (C-11′), 26.0 (C-16′), 23.6 (C-17′), 14.5 (C-18′)。以上数据与文献^[28]对照基本一致, 故该化合物确定为octadecadienoic acid-2,3-dihydroxypropyl ester。

3　活性测试

参考文献^[29-31]方法采用PNPG法测定从铁棍山药皮中分离出来的单体化合物的α-葡萄糖苷酶抑制活性。配制0.1 mol·L^-1 PBS、0.5 U·mL^-1 α-葡萄糖苷酶溶液、2.5 mmol·L^-1 PNPG溶液、0.2 mol·L^-1 Na₂CO₃终止液以及10% DMSO溶液。

依次在96孔板中加入PBS、10% DMSO溶液、不同浓度的样品或阳性药物和α-葡萄糖苷酶后摇匀, 在37 ℃的恒温培养箱中孵育15 min。然后, 在每个孔中加入20 μL PNPG (2.5 mmol·L^-1), 摇匀, 再次放入37 ℃的恒温培养箱中培养15 min。最后, 在每个孔中加入0.2 mol·L^-1碳酸钠溶液80 μL停止反应, 使用酶标仪在405 nm处测定吸光度(A)值。通过GraphPad Prism 9.0软件计算各组数据并进行统计学分析。按下列公式计算各样品对α-葡萄糖苷酶的抑制率: 抑制率% = [1-(A_样品-A_背景) / (A_阴性-A_空白)] × 100%

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2025年第60卷第12期

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doi: 10.16438/j.0513-4870.2025-0981

接收时间：2025-08-18
首发时间：2026-09-20
出版时间：2025-12-12

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收稿日期：2025-08-18
修回日期：2025-09-25

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¹上海中医药大学中药研究所, 上海 201203

²上海市中医药国际标准化研究院, 上海 201203

³安庆医药高等专科学校药学院, 安徽皖西南特色中药资源创新应用重点实验室, 安徽安庆 246052

⁴河南焦作市温县农业科学研究所, 河南焦作 454850

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侴桂新, E-mail: chouguixinzyb@126.com

许红涛, E-mail: xht8710@163.com

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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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Position	1		2
Position	δ_C	δ_H (J in Hz)	δ_C	δ_H (J in Hz)
1	111.5		154.0
2	154.5		113.6	6.66, dd (8.0, 1.2)
3	99.9	6.98, s	126.7	7.00, dd (8.0, 8.0)
4	160.5		120.9	7.72, dd (8.0, 1.2)
4a	116.7		135.5
4b	126.2		116.8
5	110.2	9.21, s	159.8
6	148.9		99.2	6.42, d (2.2)
7	146.0		158.2
8	112.4	7.10, s	108.3	6.35, d (2.2)
8a	128.5		143.0
9	127.9	7.28, d (9.2)	31.4	2.72, dd (8.6, 5.0)
10	123.8	6.91, d (9.2)	22.0	2.62, dd (8.6, 5.0)
10a	135.8		125.1
1′	111.1
2′	154.4
3′	99.7	6.95, s
4′	160.6
4′a	116.5
4′b	126.5
5′	113.9	9.12, s
6′	145.3
7′	146.5
8′	112.5	7.08, s
8′a	128.1
9′	128.2	7.25, d (9.2)
10′	123.0	6.85, d (9.2)
10′a	135.8
4-OCH₃	56.3	4.18, s
5-OCH₃			55.8	3.80, s
6-OCH₃	56.1	4.05, s
4′-OCH₃	56.0	4.18, s