CN115524435B - 一种市售公丁香中印尼公丁香含量的检测方法 - Google Patents
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Abstract
本发明通过用HS‑SPME‑GC‑MS分析印尼公丁香中掺杂不同含量非印尼公丁香的样品，将该样品的HS‑SPME‑GC‑MS数据导入化学计量学软件，以纯印尼公丁香样品为母本，计算掺杂不同含量非印尼公丁香的待测样品相对于纯印尼公丁香的欧氏距离数，将欧氏距离数代入方程即可得到样品中印尼公丁香的含量。
Description
技术领域
本发明涉及一种丁香成分分析方法，具体涉及一种市售公丁香中印尼公丁香含量的检测方法。
背景技术
丁香为桃金娘科植物丁香的干燥花蕾，属药食同源中药，主产于印度尼西亚、桑给巴尔、马达加斯加、斯里兰卡等地，而作为全球丁香属植物的现代分布中心，我国丁香属植物有二十余种，主要分布在云南、海南、广西和广东等省区。丁香含有多种化学成分，其中挥发油是其主要成分，含量约为15％～20％，具有抗菌消炎、解热镇痛、抗癌、抗氧化、抗抑郁、降糖、驱虫、防腐、抗龋齿、壮阳等多种作用。
丁香含丁香酚等天然活性物质，不仅具有浓郁的香气，而且在抑菌、抗氧化等方面效果显著，广泛应用在香精香料，烹饪饮食，医药保健等领域。丁香挥发油在食品、香精香料、医药等行业具有多种应用，在医疗方面早已广泛应用于牙科，以治疗牙齿感染和牙龈疼痛，在各种食品中用作天然防腐剂、着色剂和香料，此外丁香挥发油在烟草工业中的应用也比较广泛，如用于烟草储藏工程中的抑霉剂和驱虫剂，以及烟草调香过程中的香精香料等。
印尼等热带地区出产的公丁香品质较好，价格也较贵，市售公丁香良莠不齐，用非印尼公丁香掺杂到印尼产的公丁香里的情况居多。因此有必要对市售公丁香中印尼公丁香含量进行检测。
为了解决以上问题，提出本发明。
发明内容
本发明目的通过以下技术方案实现。
本发明提供了一种市售公丁香中印尼公丁香含量的检测方法，其包括以下步骤：
步骤(1)：用HS-SPME-GC-MS分析印尼公丁香中掺杂不同含量非印尼公丁香的样品；
步骤(2)：欧式距离计算
将步骤(1)中所得的印尼公丁香中掺杂不同含量非印尼公丁香的样品的HS-SPME-GC-MS数据，导入化学计量学软件，以纯印尼公丁香样品为母本，计算印尼公丁香中掺杂不同含量非印尼公丁香的样品的欧氏距离；
步骤(3)：基于以下欧氏距离回归方程计算待测样品中印尼公丁香的含量Y＝-0.11643X+97.83241
其中，X为掺杂不同含量非印尼公丁香的待测样品相对于纯印尼公丁香的欧氏距离数，Y为待测样品中印尼公丁香的百分含量。
优选地，步骤(1)中所取样品平均分成份数均不小于6份，每份不少于1克。
优选地，步骤(1)中仪器分析参数如下：
HS-SPME条件：SPME吸附柱采用安捷伦PDMS-7/10，平衡温度80℃，平衡时间10min，萃取时间10min，解吸附时间8min；GC条件：HP-VOC毛细柱,进样口温度260℃，分流模式进样，分流比10:1，载气为高纯He，恒流流速1.0mL/min；升温程序：初始值40℃，保持1min,以6℃/min升至220℃并保持2min；MS条件：EI电离源70eV，离子源温度230℃，四极杆温度150℃,MSD传输线温度230℃，全扫描模式，质量范围m/z 35～400，溶剂延迟3.0min。
优选地，步骤(1)中可具体包括如下步骤：
步骤(11)：收集纯印尼公丁香样品和往印尼公丁香中掺杂不同含量非印尼公丁香的样品，均匀分成若干份，每份按一定重量取样，装袋待测。
步骤(12)：取待测样品适量，经粉碎机破碎后过100目不锈钢筛。准确称取50mg待测样品置于棕色顶空瓶内，并加入10μL(0.5mg/mL)氘代甲苯(溶于正己烷)作为内标，随即旋紧瓶盖以供实验分析。每个试样做5次平行。
步骤(13)：将步骤(12)所得的样品溶液，通过直接进样的方式，进行HS-SPME-GC-MS检测。
步骤(14)：检测成分的定性：采用美国国家标准与技术研究院(NIST 17)质谱数据库进行检索比对，并按公式(1)计算保留指数用以辅助定性。
式中：RIx表示所测组分的保留指数；n为待分析组分前一正构烷烃碳原子数；tRx为待分析组分的保留时间；tRn为待分析组分前一正构烷烃的保留时间；tR(n+1)为待分析组分后一正构烷烃的保留时间。
步骤(15)：检测成分定量：使用内标法半定量分析。各挥发性组分含量按式(2)进行计算。
式中：Ci表示所测挥发性组分的含量；Ai为各个化合物的峰面积；A0表示内标物的峰面积；M0表示内标物质的质量；M为所称取试样的质量。
当然，步骤(1)也可以用其他取样条件、样品前处理条件或数据处理方法，只要能符合检测原理把各物质的含量检测出来就行。
相对于现有技术，本发明具有以下有益效果：
1、本发明首次通过HS-SPME-GC-MS分析对市售公丁香样品中印尼公丁香含量进行准确计算，同时，可以对产品挥发性活性成分进行初步解析。
2、本发明首次通过建立欧氏距离回归方程计算市售公丁香样品中印尼公丁香的含量，该方法简便，只需要计算掺杂不同含量非印尼公丁香的待测样品相对于纯印尼公丁香的欧氏距离值，并将欧氏距离值代入方程即可得到样品中印尼公丁香的含量，且结果可靠，能够在实际生活中得到广大应用。
附图说明
图1为实施例1所拟合的欧氏距离-印尼公丁香百分含量曲线。
具体实施方式
下面结合具体实施例对本发明进行说明，但本发明的实施方式不限于此。实施例中未注明具体条件的实验方法,通常按照常规条件以及手册中所述的条件,或按照制造厂商所建议的条件所用的通用设备、材料、试剂等，如无特殊说明,均可从商业途径得到。
实施例1
分别选取纯印尼公丁香和往印尼公丁香中掺杂非印尼公丁香得到印尼公丁香含量分别为90％、70％、50％、30％的各3个样品，按照上述步骤(1)-步骤(2)，分别得到相应HS-SPME-GC-MS数据和欧氏距离结果如下表1和表2所示：
表1样品HS-SPME-GC-MS数据(mg/kg)
*注数据为3个样品平均值
表2不同百分含量的印尼公丁香样品的欧氏距离数据
| 100％-1 | 100％-2 | 100％-3 | |
| 100％-1 | 0.00 | 4.16 | 13.95 |
| 100％-2 | 4.16 | 0.00 | 13.30 |
| 100％-3 | 13.95 | 13.30 | 0.00 |
| 30％-1 | 627.62 | 627.51 | 633.16 |
| 30％-2 | 595.46 | 596.21 | 601.72 |
| 30％-3 | 601.75 | 602.05 | 607.58 |
| 50％-1 | 379.21 | 379.12 | 385.49 |
| 50％-2 | 377.11 | 377.19 | 383.92 |
| 50％-3 | 368.63 | 368.57 | 374.76 |
| 70％-1 | 212.94 | 213.05 | 221.05 |
| 70％-2 | 195.50 | 195.82 | 203.91 |
| 70％-3 | 209.09 | 209.79 | 218.08 |
| 90％-1 | 93.52 | 95.42 | 104.07 |
| 90％-2 | 67.34 | 65.66 | 69.23 |
| 90％-3 | 83.69 | 84.69 | 93.34 |
将印尼公丁香的不同百分含量和不同百分含量的印尼公丁香样品的欧氏距离数据导入软件拟合得到线性方程：
Y＝-0.11643X+97.83241，R2＝0.98069
其中，X为掺杂不同含量非印尼公丁香的待测样品相对于纯印尼公丁香的欧氏距离数，Y为待测样品中纯印尼公丁香的百分含量。
实施例2
为了验证本方法的有效性，按照实施例1重新制备印尼公丁香含量分别为92％、83％、75％、64％、51％、40％和36％的掺杂公丁香。按照步骤(1)-步骤(2)进行分析得到欧氏距离，再按照步骤(3)计算公丁香的百分含量，结果如下表3所示：
表3预测数据与真实数据
实验结果表明，本发明方法计算出的掺杂非印尼公丁香样品中印尼公丁香含量值与该样品实际的印尼公丁香含量值基本一致，表明本发明方法具有较好的可靠性。
Claims (2)
1.一种市售公丁香中印尼公丁香含量的检测方法，其特征在于，包括以下骤：
步骤(1)：用HS-SPME-GC-MS分析印尼公丁香中掺杂不同含量非印尼公丁香的样品，仪器分析参数如下：
HS-SPME条件：SPME吸附柱采用安捷伦PDMS-7/10，平衡温度80℃，平衡时间10min，萃取时间10min，解吸附时间8min；GC条件：HP-VOC毛细柱,进样口温度260℃，分流模式进样，分流比10:1，载气为高纯He，恒流流速1.0mL/min；升温程序：初始值40℃，保持1min,以6℃/min升至220℃并保持2min；MS条件：EI电离源70eV，离子源温度230℃，四极杆温度150℃,MSD传输线温度230℃，全扫描模式，质量范围m/z 35～400，溶剂延迟3.0min；
步骤(2)：欧式距离计算
将步骤(1)中所得的印尼公丁香中掺杂不同含量非印尼公丁香的样品的HS-SPME-GC-MS数据，导入化学计量学软件，以纯印尼公丁香样品为母本，计算印尼公丁香中掺杂不同含量非印尼公丁香的样品的欧氏距离数；
步骤(3)：基于以下欧氏距离回归方程计算待测样品中印尼公丁香的含量Y＝-0.11643X+97.83241
其中，X为掺杂不同含量非印尼公丁香的待测样品相对于纯印尼公丁香的欧氏距离数，Y为待测样品中印尼公丁香的百分含量。
2.根据权利要求1所述的方法，其特征在于，步骤(1)中所取样品平均分成份数均不小于6份，每份不少于1克。
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