第 5 期 王茂媛等:基于 UPLC-Q-TOF-MS 技术的益智种子和果皮成分分析 1065
by the gradient elution method with waters ACQUITY UPLC HSS T3 (100 mm×2.1 mm, 1.8 μm), the mobile phase
consisted of 0.1% formic acid and 0.01% formic acid acetonitrile, with the flow rate of 0.3 mL/min. Mass spectrometry
was applied for the qualitative analysis with ESI ion source. Through molecular feature extraction (MFE), Masslynx
software was then used to process the original MS data. Furthermore, the structures of the compounds were speculated
according to the MS fragmentation patterns and confirmed by comparison with reference standards. Thirty-two and fifty
compounds were identified from the seeds and peels respectively, including flavonoids, phenolic acids, saccharides,
fatty acids and terpenes. 58 compounds were isolated from the plant for the first time. The main constituents of the seeds
were phenolic acids (11 compounds), which were representative constituents of the seeds, accounting for one third of
the total identified structural compounds of the seeds. On the contrary, there were few phenolic acids in the peels. The
main constituents of the peels were flavonoids (19 compounds) of various kinds, accounting for one third of the total
identified structural compounds of the peels. On the contrary, there was only one flavonoid identified in the seeds. A
total of 4 components were found both in the nonvolatile component of the ethanol extract in the seeds and peels, including monosaccharides of D-gluconic acid and D-glucopyranuronic acid, disaccharide of sucrose, flavonoid of
chysin. The results showed that the nonvolatile components of the seeds were lesser than that of the peels. The chemical
constituents of the seeds and peels were found to be quite different. The main constituents of the seeds were phenolic
acids, and the main constituents of the fruit were flavonoids and terpenoids. It should be treated differently in comprehensive utilization and quality control of the seeds and peels of A. oxyphylla.
Keywords: UPLC-Q-TOF-MS; seeds and peels of Alpinia oxyphylla; chemical constituents
DOI: 10.3969/j.issn.1000-2561.2022.05.021
益智(Alpinia oxyphylla Miq.)为姜科山姜属
植物,是我国著名的四大南药之一,也是海南省
道地药材,在广西、广东、福建、云南等省(区)
也有分布[1]。益智以干燥成熟果实入药,商品名
为益智仁、益智子,为我国历版药典收载,具有
暖肾固精缩尿,温脾止泻摄唾等功效,用于肾虚
遗尿,小便频数,遗精白浊,脾寒泄泻,腹中冷
痛,口多唾涎等症[2]。益智是民间常用药材,也是
卫计委公布的药食同源原料,被广泛应用在我国许
多著名方剂、中成药或保健品中,如缩泉丸[3-4]、
遗溺汤、补原丸、益智酒[5]、益智调味酱[6-7]、益
智茶[8]等。已有研究表明益智含有挥发油类、二
苯庚烷类、黄酮类、萜类、甾醇及其苷类等化学
成分[9-12],具有保护神经、抗氧化应激、抗糖尿
病肾病、改善肠胃功能、镇静催眠、抗肿瘤、抗
菌等功效[10, 13-18]。益智在现代临床上有去壳(果
皮)和带壳两种使用方法,然而历版中国药典记
载益智(果实)作为饮片炮制时,需除去外壳(果
皮),以捣碎的种子或种子团残瓣入药或进一步炮
制使用,约占干燥果实 29%~31%的果皮作为废
弃物被丢弃,存在益智药材资源浪费的问题[19]。
近年来,关于益智种子和果皮化学成分的比较研
究多集中在挥发油[20-21]、总黄酮[22]、总多糖[23]
和低聚糖[24]等主要成分的含量对比分析,而采用
HPLC 技术对益智种子和果皮化学成分的对比分
析较少[25],尚未弄清二者的化学物质组成和区
别,尤其是非挥发性成分组成及对比更鲜见报道。
因此,为科学发掘益智资源的利用价值,有必要
明晰益智种子和果皮的非挥发性化学物质组成和
区别。基于此,在前期研究基础上[26],笔者首次
采用 UPLC-Q-TOF-MS 技术建立与现有中药质量
控制发展水平相符合的检测方法,完成对益智种
子和果皮乙醇提取物非挥发性化学成分的定性分
析,通过对比分析传统药用部位益智种子和废弃
物益智果皮非挥发性化学成分类别和组成,以阐
明益智资源的内涵,为明确其非传统药用部位的
开发利用价值提供科学依据,同时也为益智炮制
和临床使用及其相关产品的开发,完善质量标准
提供参考。
1 材料与方法
1.1 材料
1.1.1 植物材料 益智果实于 2018年 5月采摘于
中国热带农业科学院热带作物品种资源研究所农
业农村部热带药用植物种质圃,经王祝年研究员
鉴定为姜科山姜属植物益智(Alpinia oxyphylla
Miq.)的干燥成熟果实。人工剥离,分别获得益
智种子和益智果皮。
1.1.2 仪器与试剂 Xevo G2-XS QTof 液质联用
仪,美国 Waters 公司;Secura513-1CN 精密天平,
德国 Sartorius 公司;KQ3200DE 超声波清洗器,
昆山市超声仪器有限公司;5810R 高速冷冻离心