基于太赫兹辐射的甘草主成分光谱分析

燕芳; 张俊林; 刘成毫; 于洋

基于太赫兹辐射的甘草主成分光谱分析

燕芳^1,,
张俊林^1, ,,
刘成毫¹,
于洋^{2, 3}

1.
内蒙古科技大学信息工程学院，内蒙古包头 014010
2.
北京科技大学自动化学院，北京 100083
3.
北京市工业波谱成像工程技术研究中心，北京 100083

基金项目:

国家自然科学基金项目 61463041

内蒙古自然基金项目 2018MS06020

详细信息

作者简介:
燕芳（1980-），女，副教授，博士，主要研究领域为太赫兹技术及应用。E-mail: 0472yanfang@163.com

通讯作者:
张俊林（1994-），男，硕士研究生，主要研究方向为太赫兹时域光谱技术。E-mail: zhangjunlin88888@163.com

中图分类号: O657.3
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- 被引次数: 0
出版历程
- 收稿日期: 2020-04-30
- 修回日期: 2020-12-30
- 刊出日期: 2021-04-02

Principal Component Spectrum Analysis of Licorice Based on Terahertz Radiation

YAN Fang^1
,,
ZHANG Junlin^{1
, ,},
LIU Chenghao¹,
YU Yang^{2, 3}

1.
School of Information Engineering, Inner Mongolia University of Science and Technology, Baotou 014010, China
2.
School of Automation, University of Science and Technology Beijing, Beijing 100083, China
3.
Beijing Industrial Spectrum Imaging Engineering Technology Research Center, Beijing 100083, China

摘要

摘要: 采用透射式太赫兹时域光谱系统测试了甘草主成分甘草酸、甘草次酸以及甘草苷的太赫兹光谱，发现甘草酸、甘草次酸以及甘草苷在0.3~1.72 THz频段内具有明显的吸收特征，此频段内它们的太赫兹吸收峰峰位接近、吸收谱谱线相似。利用量子化学方法模拟甘草酸的太赫兹吸收谱，并与实验谱进行对比指认完成对3种单质的定性分析工作。本文分别采用基于DFT和PM3模型，完成对甘草酸单分子构型的结构优化与频率计算。结果表明，两种方法得到的太赫兹模拟吸收峰与实验吸收峰基本吻合，而且基于DFT模型得到的太赫兹模拟吸收谱波形与实验谱更为接近。最后选取了甘草酸的特征吸收峰1.655 THz及其附近6个数值点的太赫兹吸收系数，将其取平均值后与浓度进行了一元线性回归拟合，拟合结果从理论上验证了甘草酸太赫兹吸收谱符合朗伯比尔定律。
- 太赫兹时域光谱 /
- 甘草酸 /
- 一元线性回归 /
- 量子化学
Abstract: In this study, a transmission terahertz time-domain spectrum system was used to test the terahertz spectra of glycyrrhizic acid, glycyrrhetic acid, and glycyrrhizin as the main components of glycyrrhiza (licorice). The characteristics of these licorice constituents and their terahertz absorption peaks were found to be close to each other and their absorption spectra were similar. A quantum chemistry method was used to simulate the terahertz absorption spectrum of glycyrrhizic acid; this spectrum was then compared with the experimental spectrum to perform a qualitative analysis of the three elements. In this study, based on the density functional theory (DFT) and PM3 models, a single molecular configuration of glycyrrhizic acid was introduced for structural optimization and frequency calculation. The results showed that the terahertz simulated absorption peaks obtained by the two methods coincided with the experimental absorption peaks, and the terahertz simulated absorption spectrum waveforms obtained based on the DFT model were closer to those of the experimental spectrum. Finally, the characteristic absorption peak of glycyrrhizic acid at 1.655THz and the terahertz absorption coefficients of six nearby numerical points were selected, and the average value was used to perform a one-dimensional linear regression fitting with the concentration. The fitting results verified the licorice theoretically, and the acid terahertz absorption spectrum conformed to Lambert's law.
- terahertz time-domain spectroscopy /
- glycyrrhizic acid /
- univariate linear regression /
- quantum chemistry

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图 1 三种单质的太赫兹吸收谱

Figure 1. THz absorption spectrum of three simple substances

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图 2 甘草酸的分子构型

Figure 2. Glycyrrhizic acid molecular configuration

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图 3 甘草酸实验光谱与PM3、DFT计算谱对比

Figure 3. Comparison of glycyrrhizic acid experimental spectrum with PM3, DFT calculated spectrum

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图 4 不同浓度的甘草酸太赫兹吸收谱

Figure 4. THz absorption spectrum of glycyrrhizinate with different contents

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图 5 一元线性回归预测模型

Figure 5. Univariate linear regression prediction model

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表 1 样品配比信息

Table 1. Sample Mixing Information

Sample	Sample number	Powder/mg	Pill weight/mg	Thickness/mm	Sample proportion/%
Glycyrrhizic acid (gcs)	gcs1	152.7	144.3	1.3	40
	gcs2	157.4	152.7	1.4	40
	gcs3	162.9	153.2	1.42	40
	gcs4	159.6	154.2	1.4	40
	gcs5	143.5	122.8	1.1	40
Liquiritin (gcg)	gcg1	157.8	152.3	1.3	45
	gcg2	159.5	152.8	1.32	45
	gcg3	162.6	154.8	1.3	45
	gcg4	157.4	149.2	1.28	45
	gcg5	134.7	126.6	1.1	45
Glycyrrhetnic acid (gccs)	gccs1	155.9	150.6	1.3	45
	gccs2	160.0	143.4	1.32	45
	gccs3	163.2	157.4	1.4	45
	gccs4	160.4	151.8	1.4	45
	gccs5	158.9	151.3	1.44	45

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表 2 三种样品吸收峰位

Table 2. Peak absorption of three samples THz

No.	1	2	3	4	5	6	7	8	9
Glycyrrhizic acid (gcs)	1.131	1.440	1.561	1.610	1.655	1.704	-	-	-
Liquiritin (gcg)	0.349	0.433	1.437	1.518	1.564	1.606	1.662	1.714	-
Glycyrrhetnic acid (gccs)	0.342	0.427	1.004	1.131	1.44	1.574	1.613	1.662	1.714

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表 3 不同浓度甘草酸样品的配比信息

Table 3. Proportion information of glycyrrhizic acid samples with different concentrations

Sample number	Powder/mg	Pill weight/mg	Thickness/mm	Sample proportion/%	Concentration/(mol/L)
gcs01	158.4	155.7	1.28	20	0.312
gcs02	161.2	158.7	1.43	30	0.426
gcs03	159.6	154.2	1.4	40	0.574

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表 4 1.655 THz及其附近6个频率点的吸收系数值

Table 4. Absorption coefficient values at 1.655 THz and 6 frequency points around it

Frequency/THz	Absorption/(gcs01)	Absorption/ (gcs02)	Absorption/ (gcs03)
1.646	10.935	19.566	34.327
1.649	11.026	20.573	35.255
1.652	11.074	21.274	36.572
1.655	11.083	21.473	38.239
1.659	11.061	21.276	36.482
1.662	11.017	20.876	34.127
1.665	10.962	20.404	33.539
Average absorption	11.023	20.777	35.506

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表 5 浓度预测值及相对误差

Table 5. Concentration prediction values and relative errors

Sample number	gcs01	gcs02	gcs03
Prediction/(mol/L)	0.316	0.420	0.577
Real/(mol/L)	0.312	0.426	0.574
Relative error/%	1.28	1.41	0.52

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