Article(id=1193558474316542436, tenantId=1146029695717560320, journalId=1189982191388893191, issueId=1193558470239678932, articleNumber=null, orderNo=null, doi=10.16438/j.0513-4870.2024-0737, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1722268800000, receivedDateStr=2024-07-30, revisedDate=1726761600000, revisedDateStr=2024-09-20, acceptedDate=null, acceptedDateStr=null, onlineDate=1762496115520, onlineDateStr=2025-11-07, pubDate=1736611200000, pubDateStr=2025-01-12, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1762496115520, onlineIssueDateStr=2025-11-07, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1762496115520, creator=13701087609, updateTime=1762496115520, updator=13701087609, issue=Issue{id=1193558470239678932, tenantId=1146029695717560320, journalId=1189982191388893191, year='2025', volume='60', issue='1', pageStart='1', pageEnd='244', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1762496114549, creator=13701087609, updateTime=1764224942173, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1200809698921402865, tenantId=1146029695717560320, journalId=1189982191388893191, issueId=1193558470239678932, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1200809698921402866, tenantId=1146029695717560320, journalId=1189982191388893191, issueId=1193558470239678932, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=191, endPage=195, ext={EN=ArticleExt(id=1193558474522063337, articleId=1193558474316542436, tenantId=1146029695717560320, journalId=1189982191388893191, language=EN, title=A new glycoside from Alstonia mairei Lévl., columnId=1190335348761793317, journalTitle=Acta Pharmaceutica Sinica, columnName=Original Articles, runingTitle=null, highlight=null, articleAbstract=

Nine compounds were isolated and purified from 90% ethanol extract of Alstonia mairei Lévl by using various chromatographic methods, including silica gel, SephadexLH-20, MCI Gel and ODS column chromatography, combined with semi-preparative liquid phase separation methods. Modern spectroscopic methods (1D and 2D NMR, UV, IR, MS, etc.) were used to identify the structures of the isolated compounds. They were identified as mairoside A (1), 3′, 6-di-O-sinaloylsucrose (2), myristic acid (3), methyl myristate (4), ethyl myristate (5), 3, 4, 5-trimethoxycinnamic acid (6), 3, 4, 5-trimethoxybenzoic acid (7), vinoline (8), kaempferol-3-O-rutinoside (9), among which compound 1 is a new glycoside, compounds 4 and 5 are new natural products, and the nuclear magnetic data of compound 4 were reported for the first time.

, correspAuthors=Ying-ying SI, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright ©2025 Acta Pharmaceutica Sinica. All rights reserved., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Li-ke WANG, Bing-yan LI, Zhen-zhu ZHAO, Yan-zhi WANG, Xiao-kun LI, Wei-sheng FENG, Ying-ying SI), CN=ArticleExt(id=1193558569107812920, articleId=1193558474316542436, tenantId=1146029695717560320, journalId=1189982191388893191, language=CN, title=羊角棉中1个新的糖苷类化合物, columnId=1190335348896011050, journalTitle=药学学报, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=

利用硅胶、Sephadex LH-20、MCI Gel和ODS等柱色谱, 结合半制备液相等分离方法, 从羊角棉90%乙醇提取物中分离纯化得到9个化合物。运用现代波谱学方法(1D和2D NMR、UV、IR、MS等) 对所分离得到的化合物进行结构鉴定, 分别鉴定为mairoside A (1)、3′, 6-二-O-芥子酰基蔗糖(2)、肉豆蔻醚酸(3)、肉豆蔻醚酸甲酯(4)、肉豆蔻醚酸乙酯(5)、3, 4, 5-三甲氧基桂皮酸(6)、3, 4, 5-三甲氧基苯甲酸(7)、维诺林(8)、山柰酚-3-O-芸香糖苷(9), 其中化合物1为新糖苷类化合物, 化合物45为新天然产物, 且化合物4的核磁数据为首次报道。

, correspAuthors=司盈盈, authorNote=null, correspAuthorsNote=
*司盈盈, Tel: 86-371-65962746, E-mail:
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No. δH δC   No. δH δC
1 5.51 (1H, d, J = 3.6 Hz) 93.3   3″, 5″  154.4
2 3.46 (1H, dd, J = 10.0, 3.6 Hz) 73.2 4″  143.7
3 3.69 (1H, m) 74.8 3″, 5″-OMe 3.85 (6H, s) 56.7
4 3.43 (1H, d, J = 8.9 Hz) 71.9 4″-OMe 3.81 (3H, s) 61.1
5 4.26 (1H, dd, J = 10.1, 2.9 Hz) 72.5 7″  167.6
6 4.74 (1H, dd, J = 12.0, 1.7 Hz) 65.8 1‴  126.4
  4.46 (1H, dd, J = 12.0, 4.9 Hz)        
1′ 3.66 (1H, d, J = 12.0 Hz) 65.7 2‴, 6‴ 6.93 (2H, s) 107.1
  3.60 (1H, d, J = 12.0 Hz)        
2′  105.1 3‴, 5‴  149.4
3′ 5.46 (1H, d, J = 7.8 Hz) 79.6 4‴  139.8
4′ 4.32 (1H, t, J = 7.8 Hz) 74.1 7‴ 7.69 (1H, d, J = 16.0 Hz) 148.0
5′ 3.89 (1H, m) 84.2 8‴ 6.46 (1H, d, J = 16.0 Hz) 115.4
6′ 3.76 (1H, m) 63.2 9‴  168.2
  3.71 (1H, m)        
1″   126.4 3″, 5″-OMe 3.87 (6H, s) 56.8
2″, 6″ 7.33 (2H, s) 108.2    
), ArticleFig(id=1194708071697060193, tenantId=1146029695717560320, journalId=1189982191388893191, articleId=1193558474316542436, language=CN, label=Table 1, caption=

1H (500 MHz) and 13C (125 MHz) NMR data of 1 in CD3OD

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No. δH δC   No. δH δC
1 5.51 (1H, d, J = 3.6 Hz) 93.3   3″, 5″  154.4
2 3.46 (1H, dd, J = 10.0, 3.6 Hz) 73.2 4″  143.7
3 3.69 (1H, m) 74.8 3″, 5″-OMe 3.85 (6H, s) 56.7
4 3.43 (1H, d, J = 8.9 Hz) 71.9 4″-OMe 3.81 (3H, s) 61.1
5 4.26 (1H, dd, J = 10.1, 2.9 Hz) 72.5 7″  167.6
6 4.74 (1H, dd, J = 12.0, 1.7 Hz) 65.8 1‴  126.4
  4.46 (1H, dd, J = 12.0, 4.9 Hz)        
1′ 3.66 (1H, d, J = 12.0 Hz) 65.7 2‴, 6‴ 6.93 (2H, s) 107.1
  3.60 (1H, d, J = 12.0 Hz)        
2′  105.1 3‴, 5‴  149.4
3′ 5.46 (1H, d, J = 7.8 Hz) 79.6 4‴  139.8
4′ 4.32 (1H, t, J = 7.8 Hz) 74.1 7‴ 7.69 (1H, d, J = 16.0 Hz) 148.0
5′ 3.89 (1H, m) 84.2 8‴ 6.46 (1H, d, J = 16.0 Hz) 115.4
6′ 3.76 (1H, m) 63.2 9‴  168.2
  3.71 (1H, m)        
1″   126.4 3″, 5″-OMe 3.87 (6H, s) 56.8
2″, 6″ 7.33 (2H, s) 108.2    
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羊角棉中1个新的糖苷类化合物
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王立柯 1 , 李冰燕 1 , 赵珍珠 1, 2 , 王彦志 1, 2 , 李晓坤 1, 2 , 冯卫生 1, 2 , 司盈盈 1, 2, *
药学学报 | 研究论文 2025,60(1): 191-195
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药学学报 | 研究论文 2025, 60(1): 191-195
羊角棉中1个新的糖苷类化合物
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王立柯1, 李冰燕1, 赵珍珠1, 2, 王彦志1, 2, 李晓坤1, 2, 冯卫生1, 2, 司盈盈1, 2, *
作者信息
  • 1.河南中医药大学药学院, 河南 郑州 450046
  • 2.河南省中药开发工程技术研究中心, 河南 郑州 450046

通讯作者:

*司盈盈, Tel: 86-371-65962746, E-mail:
A new glycoside from Alstonia mairei Lévl.
Li-ke WANG1, Bing-yan LI1, Zhen-zhu ZHAO1, 2, Yan-zhi WANG1, 2, Xiao-kun LI1, 2, Wei-sheng FENG1, 2, Ying-ying SI1, 2, *
Affiliations
  • 1. School of Pharmacy, Henan University of Traditional Chinese Medicine, Zhengzhou 450046, China
  • 2. Engineering and Technology Center for Chinese Medicine Development of Henan Province, Zhengzhou 450046, China
出版时间: 2025-01-12 doi: 10.16438/j.0513-4870.2024-0737
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利用硅胶、Sephadex LH-20、MCI Gel和ODS等柱色谱, 结合半制备液相等分离方法, 从羊角棉90%乙醇提取物中分离纯化得到9个化合物。运用现代波谱学方法(1D和2D NMR、UV、IR、MS等) 对所分离得到的化合物进行结构鉴定, 分别鉴定为mairoside A (1)、3′, 6-二-O-芥子酰基蔗糖(2)、肉豆蔻醚酸(3)、肉豆蔻醚酸甲酯(4)、肉豆蔻醚酸乙酯(5)、3, 4, 5-三甲氧基桂皮酸(6)、3, 4, 5-三甲氧基苯甲酸(7)、维诺林(8)、山柰酚-3-O-芸香糖苷(9), 其中化合物1为新糖苷类化合物, 化合物45为新天然产物, 且化合物4的核磁数据为首次报道。

鸡骨常山属  /  羊角棉  /  化学成分  /  糖苷  /  分离鉴定

Nine compounds were isolated and purified from 90% ethanol extract of Alstonia mairei Lévl by using various chromatographic methods, including silica gel, SephadexLH-20, MCI Gel and ODS column chromatography, combined with semi-preparative liquid phase separation methods. Modern spectroscopic methods (1D and 2D NMR, UV, IR, MS, etc.) were used to identify the structures of the isolated compounds. They were identified as mairoside A (1), 3′, 6-di-O-sinaloylsucrose (2), myristic acid (3), methyl myristate (4), ethyl myristate (5), 3, 4, 5-trimethoxycinnamic acid (6), 3, 4, 5-trimethoxybenzoic acid (7), vinoline (8), kaempferol-3-O-rutinoside (9), among which compound 1 is a new glycoside, compounds 4 and 5 are new natural products, and the nuclear magnetic data of compound 4 were reported for the first time.

Alstonia  /  Alstonia mairei Lévl.  /  chemical composition  /  glycoside  /  separation and structural characterization
王立柯, 李冰燕, 赵珍珠, 王彦志, 李晓坤, 冯卫生, 司盈盈. 羊角棉中1个新的糖苷类化合物. 药学学报, 2025 , 60 (1) : 191 -195 . DOI: 10.16438/j.0513-4870.2024-0737
Li-ke WANG, Bing-yan LI, Zhen-zhu ZHAO, Yan-zhi WANG, Xiao-kun LI, Wei-sheng FENG, Ying-ying SI. A new glycoside from Alstonia mairei Lévl.[J]. Acta Pharmaceutica Sinica, 2025 , 60 (1) : 191 -195 . DOI: 10.16438/j.0513-4870.2024-0737
羊角棉(Alstonia mairei Lévl.) 又名鸡舌头树、闹狗药、见血飞, 为夹竹桃科(Apocynaceae) 鸡骨常山属(Alstonia) 植物, 是我国特有种, 产于云南、贵州、四川。根、叶可供药用, 具有清热、解毒、止痛、止血和排脓生肌等功效, 可用于治疗外伤出血和疮毒等[1]。已报道的羊角棉化学成分类型主要包括单萜吲哚生物碱类、黄酮类、三萜类以及香豆素类等, 其中单萜吲哚生物碱类含量最高, 是其主要成分, 也是鸡骨常山属植物的特征性成分, 具有多种生物活性, 如抗炎、抗肿瘤、乙酰胆碱酯酶抑制作用、抗氧化、神经保护作用等[2-7]。为了进一步揭示羊角棉的药效物质基础, 丰富其化学组成, 本实验对羊角棉的化学成分进行了研究, 从羊角棉中分离并鉴定了9个化合物, 结构见图 1, 其中化合物1为新糖苷类化合物, 化合物45为新天然产物, 且化合物4的核磁数据为首次报道。
化合物1为黄色油状物, [α]$ {}_{\mathrm{D}}^{20} $ -1.972 (c 0.1, MeOH), IR显示存在羟基(3 452 cm-1)、羰基(1 708 cm-1) 和苯环(1 593、1 516 cm-1) 的特征吸收峰; UV显示在206 nm处有最大吸收峰。HR-ESI-MS给出准分子离子峰m/z 765.220 1 [M+Na]+, 计算值为765.221 2, 推测其分子式为C33H42O19, 不饱和度为13。化合物11H NMR (CD3OD, 500 MHz) 谱(表 1) 显示一组3, 5-二甲氧基-4-羟基肉桂酰基氢信号[δH 3.87 (6H, s, 3‴-OMe, 5‴-OMe)、6.46 (1H, d, J = 16.0 Hz, H-8‴)、6.93 (2H, s, H-2‴, H-6‴)、7.69 (1H, d, J = 16.0 Hz, H-7‴)], 由双键的偶合常数J = 16.0 Hz可知双键为反式构型; 一组呋喃果糖基氢信号[δH 3.60 (1H, d, J = 12.0 Hz, H-1′a)、3.66 (1H, d, J = 12.0 Hz, H-1′b)、3.71 (1H, m, H-6′a)、3.76 (1H, m, H-6′b)、3.89 (1H, m, H-5′)、4.32 (1H, t, J = 7.8 Hz, H-4′)、5.46 (1H, d, J = 7.8 Hz, H-3′)]; 一组吡喃葡萄糖基氢信号[δH 3.43 (1H, d, J = 8.9 Hz, H-4)、3.46 (1H, dd, J = 10.0, 3.6 Hz, H-2)、3.69 (1H, m, H-3)、4.26 (1H, dd, J = 10.1, 2.9 Hz, H-5)、4.46 (1H, dd, J = 12.0, 4.9 Hz, H-6a)、4.74 (1H, dd, J = 12.0, 1.7 Hz, H-6b)、5.51 (1H, d, J = 3.6 Hz, H-1)]; 和一组3, 4, 5-三甲氧基苯甲酰基氢信号[δH 3.81 (3H, s, 4″-OMe)、3.85 (6H, s, 3″-OMe, 5″-OMe)、7.33 (2H, s, H-2″, H-6″)]。13C NMR (CD3OD, 125 MHz) 谱共显示出33个碳信号, 包括14个芳香碳信号(归属为两个苯环和一个双键)、2个酯羰基碳信号、5个甲氧基碳信号和12个连氧脂肪碳信号(归属为一个葡萄糖和一个果糖)。
在HMBC谱中(图 2), H-1与C-2′相关, 提示葡萄糖1位与果糖的2′位相连; H-6、H-6″与C-7″相关, 证明3, 4, 5-三甲氧基苯甲酰基的7″位与葡萄糖的6位相连; H-7‴、H-8‴、H-3′与C-9‴相关, 说明3, 5-二甲氧基-4-羟基肉桂酰基的9‴位与果糖的3′位相连, 由此确定了该化合物的平面结构。由葡萄糖端基氢的偶合常数J = 3.6 Hz和果糖2′位碳的化学位移值δC 105.1确定葡萄糖和果糖端基碳的相对构型分别为αβ[8]。通过酸水解、衍生化后测定LC-MS确定了葡萄糖和果糖的绝对构型均为D型。综上, 确定了化合物1的结构为(3-O-sinapoyl)-β-D-fructofuranosyl-(6-O-3, 4, 5-trimethoxybenzoyl)-α-D-glucopyranoside, 命名为mairoside A。
TripleTOF 6600型高效液相色谱-高分辨质谱联用仪(美国AB SCIEX公司); AM-500 MHz核磁共振谱用超导核磁共振仪(TMS做内标, 德国Bruker公司); EVO300紫外分光光度计和Nicolet IS10红外光谱仪(美国Thermo Scientific公司); LC-52型半制备液相色谱仪(赛谱锐思北京科技有限公司); MCP 5100型旋光仪(奥地利Anton Paar); RE-5210A型旋转蒸发仪(上海亚荣生化仪器厂); N-1100型旋转蒸发仪和EYELACA-3310型低温冷凝循环泵(东京理化器械株式会社); 原子型1820C型纯水机(重庆摩尔水处理设备有限公司); MCI Gel CHP-20柱色谱材料(日本三菱化学公司); SephadexLH-20柱色谱材料(Parmacia Biotech公司); 正相硅胶柱色谱材料(200~300目, 青岛海洋化工厂); YMC-Pack ODS-A色谱柱(250 mm × 20 mm, 5 μm) 和C18 ODS柱色谱材料(50 μm, 日本YMC有限公司), 色谱纯及分析纯试剂(天津四友精细化学品有限公司)。
羊角棉于2020年8月采自中国云南省昭通市巧家县, 经河南中医药大学董诚明教授鉴定为夹竹桃科鸡骨常山属植物羊角棉(Alstonia mairei Lévl.), 干燥标本保存于河南中医药大学中药药效物质基础研究室(标本号: YJM202008)。
将7.8 kg羊角棉干燥枝叶粉碎, 用90%的乙醇回流提取3次, 每次1.5 h, 减压浓缩得到浸膏, 浸膏分散在1% HCl中, 用乙酸乙酯萃取3次, 得非生物碱部位147 g; 酸水层用氨水碱化至pH 10左右, 再用乙酸乙酯萃取3次, 得到了总生物碱部位40 g; 碱水层用正丁醇萃取, 得到了正丁醇层部位158 g。
总生物碱部位40 g, 过氧化铝(中性) 柱色谱, 用二氯甲烷-甲醇系统(100∶0~0∶100) 进行梯度洗脱, 经TLC检测、紫外灯下观察, 合并后得到14个流分, 编号为流分A~N。A流分0.6 g, 过氧化铝(中性) 柱色谱, 用石油醚-丙酮系统(100∶0~0∶100) 进行梯度洗脱, 经TLC检测、紫外灯下观察, 合并得到8个流分A1~A8, A6部位过凝胶柱色谱, 以石油醚-二氯甲烷-甲醇(5∶5∶1) 为洗脱剂进行洗脱, 依次得到Fr. A6-1~Fr. A6-4, Fr. A6-3 (43.6 mg) 经半制备高效液相(0~30 min, 乙腈-水, 30%~75%) 纯化, 得到化合物4 (tR = 19.8 min; 1.0 mg) 和5 (tR = 22.9 min; 1.8 mg)。B流分2.0 g, 过ODS柱色谱, 以甲醇-水(20∶80~100∶0) 为洗脱剂进行梯度洗脱, 得到B20、B40、B60、B80、B100五个流分, 其中Fr. B60部位过凝胶柱色谱, 以甲醇为洗脱剂进行洗脱, 经TLC检识合并得到Fr. B60-1~Fr. B60-6, Fr.B60-2经半制备高效液相(乙腈-水, 44∶56) 纯化, 得到化合物8 (tR = 20.0 min; 59.6 mg)。C、D部位合并得2.6 g, 过凝胶柱色谱, 以甲醇为洗脱剂进行洗脱, 经TLC检识合并得到Fr. CD-1~Fr. CD-6, Fr. CD-4经半制备高效液相(0~35 min, 乙腈-水, 15%~90%; 35~45 min, 乙腈-水, 90%) 纯化, 得到化合物3 (tR = 15.4 min; 3.9 mg) 和化合物6 (tR = 26.3 min; 2.7 mg)。Fr. CD-2, 过ODS柱色谱, 以甲醇-水(20∶80~100∶0) 为洗脱剂进行梯度洗脱, 分别依次得到Fr. CD-2-20%、Fr. CD-2-40%、Fr. CD-2-50%、Fr. CD-2-60%、Fr. CD-2-70%、Fr. CD-2-80%、Fr. CD-2-90%, 其中Fr. CD-2-40%流分经半制备高效液相(0~45 min, 甲醇-水, 15%~85%; 45~50 min, 甲醇-水, 85%) 纯化得到化合物7 (tR = 13.6 min; 3.5 mg)。
正丁醇部位158 g过MCI柱, 用甲醇-水系统(20∶80~100∶0) 梯度洗脱, 得到G20、G30、G40、G50、G70、G100六个流分, 其中G30部位过ODS柱色谱, 用甲醇-水系统(5∶95~100∶0) 梯度洗脱, 得到G30-23%、G30-27%。G30-23%部位过凝胶柱色谱, 以甲醇为洗脱剂洗脱, 依次得到G30-23%-1~G30-23%-4, G30-23%-4经半制备高效液相(甲醇-水, 37∶63) 纯化, 得到化合物9 (tR = 48.0 min; 32.4 mg)。G30-27%部位过凝胶柱色谱, 用甲醇洗脱, 依次得到G30-27%-1~G30-27%-5, G30-27%-3经半制备高效液相(甲醇-水, 46∶54) 纯化, 得到化合物1 (tR = 27.8 min; 10.9 mg), G30-27%-4经半制备高效液相(甲醇-水, 48∶52) 纯化, 得到化合物2 (tR = 17.9 min; 11.1 mg)。
取化合物1 (大约1 mg), 加2 mol·L-1 HCl (3 mL) 在90 ℃下加热水解2.5 h。将混合物在真空下浓缩干燥后加H2O (1 mL), 再用乙酸乙酯萃取3次, 每次1 mL。乙酸乙酯层浓缩干燥, 得苷元; 水层浓缩干燥得糖。在浓缩后水层的样品加L-半胱氨酸甲酯盐酸盐(1 mg) 和吡啶(1 mL) 在60 ℃水浴下加热1.5 h, 再加入邻甲苯异硫氰酸酯(20 μL) 在60 ℃水浴下加热1.5 h。另取D-葡萄糖对照品、L-葡萄糖对照品、D-果糖对照品、L-果糖对照品进行相同的衍生化操作。将水解得到的供试品衍生物和标准品衍生物进行液质分析。液质分析条件: TripleTOF 6600 UPLC/MS (AB SCIEX); Kinetex C18 100 Å (2.6 μm, 2.1 mm × 50 mm); 梯度洗脱: 0.1%甲酸水(A)-甲醇(B), (0~28 min) 40% B; 柱温40 ℃, 流速0.3 mL·min-1; 质谱条件: 正离子模式。通过对比供试品衍生物与各标准品衍生物的保留时间和质谱数据, 从而确定了化合物1中的两个单糖结构片段分别为D-葡萄糖和D-果糖[9]
化合物1, 黄色油状物, 易溶于甲醇, [α]$ {}_{\mathrm{D}}^{20} $ -1.972 (c 0.1, MeOH), UV (MeOH) λmax (log ε) 209 (1.72)、239 (0.70)、264 (0.46)、328 (0.59) nm; IR νmax 3 452、2 925、1 708、1 593、1 516、1 459、1 338、1 126 cm-1; 1H NMR (CD3OD, 500 MHz) 和13C NMR (CD3OD, 125 MHz) 数据见表 1, HR-ESI-MS m/z 765.220 1 [M+Na]+ (计算值为C33H42O19Na+, 765.221 2)。
化合物2, 黄色油状物, 易溶于甲醇, ESI-MS m/z 777 [M+Na]+, 分子式为C34H42O19。其1H和13C NMR (CD3OD, 500 MHz) 数据与文献[10]对比, 确定化合物2为3′, 6-二-O-芥子酰基蔗糖。
化合物3, 无色针状晶体, 易溶于甲醇, ESI-MS m/z 219 [M+Na]+, 分子式为C9H8O5。其1H和13C NMR (CD3OD, 500 MHz) 数据与文献[11]对比, 确定化合物3为肉豆蔻醚酸。
化合物4, 无色晶体, 易溶于氯仿, ESI-MS m/z 233 [M+Na]+, 分子式为C10H10O51H NMR (500 MHz, CDCl3) δH 7.33 (1H, d, J = 1.4 Hz, H-6), 7.21 (1H, d, J = 1.4 Hz, H-4), 6.06 (2H, s, H-2), 3.94 (3H, s, 7-OMe), 3.89 (3H, s, 8-OMe); 13C NMR (125 MHz, CDCl3) δC 139.6 (C-1), 102.4 (C-2), 148.8 (C-3), 104.0 (C-4), 124.6 (C-5), 110.1 (C-6), 143.4 (C-7), 166.6 (C-8), 56.7 (7-OMe), 52.3 (8-OMe)。以上数据与文献[12]对比, 确定化合物4为肉豆蔻醚酸甲酯。
化合物5, 浅黄色油状物, 易溶于氯仿, ESI-MS m/z 225 [M+H]+, 分子式为C11H12O51H NMR (500 MHz, CDCl3) δH 7.33 (1H, d, J = 1.4 Hz, H-6), 7.22 (1H, d, J = 1.4 Hz, H-4), 6.05 (2H, s, H-2), 4.35 (2H, q, J = 7.1 Hz, H-1′), 3.94 (3H, s, 7-OMe), 1.38 (3H, t, J = 7.1 Hz, H-2′); 13C NMR (125 MHz, CDCl3) δC 139.5 (C-1), 102.4 (C-2), 148.8 (C-3), 104.0 (C-4), 125.0 (C-5), 110.1 (C-6), 143.4 (C-7), 166.1 (C-8), 61.2 (C-1′), 14.5 (C-2′), 56.7 (7-OMe)。以上数据与文献[12]对比, 确定化合物5为肉豆蔻醚酸乙酯。
化合物6, 无色针状结晶, 易溶于甲醇, ESI-MS m/z 261 [M+Na]+, 分子式为C12H14O5。其1H和13C NMR (CD3OD, 500 MHz) 数据与文献[13]对比, 确定化合物6为3, 4, 5-三甲氧基桂皮酸。
化合物7, 白色无定形粉末, 易溶于甲醇, ESI-MS m/z 235 [M+Na]+, 分子式为C10H12O5。其1H和13C NMR (CD3OD, 500 MHz) 数据与文献[14]对比, 确定化合物7为3, 4, 5-三甲氧基苯甲酸。
化合物8, 无色油状物, 易溶于氯仿, ESI-MS m/z 335 [M+H]+, 分子式为C21H22N2O2。其1H和13C NMR (CDCl3, 500 MHz) 数据与文献[15]对比, 确定化合物8为维诺林。
化合物9, 黄色固体, 易溶于DMSO, ESI-MS m/z 619 [M+Na]+, 分子式为C27H32O15。其1H和13C NMR (DMSO-d6, 500 MHz) 数据与文献[16]对比, 确定化合物9为山柰酚-3-O-芸香糖苷。
作者贡献: 王立柯是本文第一作者, 负责化合物分离、结构鉴定和论文撰写; 李冰燕参与药材提取和部分化合物分离纯化工作; 赵珍珠指导化合物的分离和结构鉴定工作; 王彦志指导结构鉴定和苷的水解; 李晓坤、冯卫生指导实验设计、数据处理工作; 司盈盈是本文的通讯作者, 负责整个实验的设计、指导、稿件修改及最终定稿工作。
利益冲突: 所有作者均声明无利益冲突。
  • 河南省科技攻关项目(232102310383)
  • 河南省高校科技创新团队支持计划资助(24IRTSTHN039)
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doi: 10.16438/j.0513-4870.2024-0737
  • 接收时间:2024-07-30
  • 首发时间:2025-11-07
  • 出版时间:2025-01-12
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  • 收稿日期:2024-07-30
  • 修回日期:2024-09-20
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    1.河南中医药大学药学院, 河南 郑州 450046
    2.河南省中药开发工程技术研究中心, 河南 郑州 450046

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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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