基于偏最小二乘法的近红外光谱测定八角中反式茴香脑和莽草酸

doi:10.3969/j.issn.0253-2417.2023.04.006

摘要/Abstract

摘要：

采用偏最小二乘法(PLS)建立八角中反式茴香脑和莽草酸含量的近红外光谱定量分析模型。利用近红外光谱技术采集八角粉末的近红外光谱图(NIR)，以高效液相色谱法测定的八角中反式茴香脑和莽草酸质量分数作为参考值，经过光谱处理软件将近红外光谱图与质量分数参考值进行关联，反式茴香脑的定量分析模型采用二阶导数作为预处理方法，以7 502~5 446.2和4 601.5~4 246.7 cm^-1为波数范围，维数为10；莽草酸的定量分析模型采用一阶导数加直线减法作为预处理方法，以7 502~6 098.1和5 450.1~4 597.6 cm^-1为波数范围，维数为8。结果表明：建立的八角中反式茴香脑和莽草酸含量的快速无损定量检测模型的决定系数(R²)分别为90.86%和93.13%，校正集的内部交叉检验均方根误差(RMSECV)分别为0.158和0.285，验证集的均方根误差(RMSRP)分别是0.068 7和0.171，配对T检验P值分别为0.761和0.194，均大于0.05，测量值与参考值偏差较小，建立的模型能较准确地测定八角中反式茴香脑和莽草酸的含量。

关键词: 偏最小二乘法, 近红外光谱, 定量模型, 反式茴香脑, 莽草酸

Abstract:

The partial least squares(PLS) method was used to establish the near infrared quantitative analysis model for the contents of trans-anethole and shikimic acid in Illicium verum. The near-infrared spectrogram(NIR)of star anise powder was collected by near-infrared spectroscopy, and the mass fractions of trans-anethole and shikimic acid in star anise powder were determined by high performance liquid chromatography(HPLC) as reference values. The NIR was correlated with the reference values of mass fractions through spectral processing software, and the quantitative analysis model of each component to be measured was established. The spectra of trans-anethole were pretreated by the second derivative, the wave number ranges were 7 502-5 446.2 and 4 601.5-4 246.7 cm^-1 and the dimension was 10; the spectra of shikimic acid were pretreated by the first derivation plus linear substraction with 7 502-6 098.1 and 5 450.1-4 597.6 cm^-1 as wave number ranges, and the dimension was 8. The results showed that the determination coefficients(R²) of the established rapid nondestructive quantitative detection models for the contents of trans-anethole and shikimic acid in I. verum were 90.86% and 93.13%, respectively. The root mean square errors of cross-validation(RMSECV) of the correction set were 0.158 and 0.285, the root mean square errors of the verification set(RMSRP) were 0.068 7 and 0.171, and the paired T-test P values were 0.761 and 0.194, respectively, both greater than 0.05. The deviation between the measured value and the reference value was small. The established model could accurately determine the contents of trans-anethole and shikimic acid in I. verum.

Key words: partial least squares, near infrared spectroscopy, quantitative model, trans-anethole, shikimic acid

中图分类号:

TQ35
R917

黎强, 周颖, 刘佳明, 梁淼凤. 基于偏最小二乘法的近红外光谱测定八角中反式茴香脑和莽草酸[J]. 林产化学与工业, 2023, 43(4): 38-46.

Qiang LI, Ying ZHOU, Jiaming LIU, Miaofeng LIANG. Determination of trans-Anethole and Shikimic Acid Content in Star Anise by Near Infrared Spectroscopy Based on Partial Least Squares Method[J]. Chemistry and Industry of Forest Products, 2023, 43(4): 38-46.

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参考文献 17

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序号 No.	反式茴香脑/% trans-anethole	莽草酸/% shikimic acid	序号 No.	反式茴香脑/% trans-anethole	莽草酸/% shikimic acid	序号 No.	反式茴香脑/% trans-anethole	莽草酸/% shikimic acid
1	5.47	6.32	19	6.53	6.49	37	6.62	8.97
2	5.75	6.69	20	5.63	6.68	38	6.09	8.70
3	6.54	6.40	21	5.88	7.00	39	7.15	9.18
4	5.84	6.58	22	5.67	7.76	40	5.40	7.08
5	6.43	6.79	23	6.80	5.35	41	6.89	6.62
6	5.91	6.32	24	6.14	6.34	42	5.62	6.81
7	6.89	8.39	25	5.98	5.78	43	6.63	8.58
8	6.25	5.97	26	5.69	6.06	44	5.96	6.76
9	5.95	5.98	27	5.02	4.38	45	6.60	6.06
10	5.97	8.34	28	5.64	6.58	46	5.71	6.81
11	5.97	6.48	29	6.06	7.27	47	5.60	6.14
12	6.10	5.94	30	7.13	6.07	48	5.13	6.33
13	6.01	8.04	31	5.69	5.94	49	6.03	8.32
14	5.70	5.96	32	5.88	6.48	50	5.77	7.93
15	6.62	7.87	33	6.12	8.34	51	6.05	8.29
16	6.07	5.45	34	5.99	7.72	52	5.32	6.50
17	6.08	8.32	35	6.14	8.47
18	5.50	5.69	36	5.91	7.28

成分 component	波数范围/cm^-1 wavenumber range	R²/%	RMSECV
反式茴香脑 trans-anethole	7 502~5 446.2，4 601.5~4 246.7	90.86	0.158
	6 101.9，5 446.2	83.19	0.214
	6 101.9，4 246.7	87.04	0.188
莽草酸 shikimic acid	7 502~6 098.1，5 450.1~4 597.6	93.13	0.285
莽草酸 shikimic acid	11 995.5~6 098.1，5 450.1~4 597.6	89.30	0.355

成分 component	预处理方法 preprocessing method	R²/%	RMSECV
反式茴香脑 trans-anethole	一阶导数first derivative	77.07	0.251
	二阶导数second derivative	90.86	0.158
	矢量归一化vector normalization	62.96	0.318
	最小-最大归一化min-max ormalization	60.42	0.329
莽草酸 shikimic acid	一阶导数first derivative	87.82	0.379
	二阶导数second derivative	81.17	0.471
	矢量归一化vector normalization	75.38	0.539
	最小-最大归一化min-max ormalization	71.81	0.577
	一阶导数+直线减法first derivative+straight line subtraction	93.13	0.285

项目project	维数rank	R²/%	RMSECV
反式茴香脑 trans-anethole	5	41.67	0.369
	7	67.61	0.283
	8	76.75	0.244
	9	88.33	0.176
	10	90.86	0.158
莽草酸 shikimic acid	5	86.67	0.397
	7	92.68	0.294
	8	93.13	0.285
	9	90.44	0.336
	10	80.59	0.479

序号 No.	反式茴香脑trans-anethole			莽草酸shikimic acid
序号 No.	HPLC测定值/% HPLC measured value	NIR测定值/% NIR measured value	偏差/% deviation	HPLC测定值/% HPLC measured value	NIR测定值/% NIR measured value	偏差/% deviation
2	5.75	5.932	0.032	6.69	6.297	-0.058
3	6.54	6.646	0.016	6.40	6.201	-0.031
5	6.43	6.247	-0.029	6.79	6.605	-0.028
7	6.89	6.769	-0.017	8.39	8.267	-0.015
9	5.95	6.061	0.019	5.98	6.473	0.083
11	5.97	5.993	0.004	6.48	5.718	-0.118
12	6.10	6.177	0.012	5.94	5.767	-0.029
14	5.70	5.541	-0.028	5.96	6.404	0.075
15	6.62	5.918	-0.107	7.87	7.900	0.004
17	6.08	6.02	-0.010	8.32	7.680	-0.077
19	6.53	6.387	-0.022	6.49	6.416	-0.012
22	5.67	5.801	0.024	7.76	7.737	-0.003
24	6.14	5.867	-0.045	6.34	6.151	-0.029
26	5.69	5.874	0.032	6.06	6.565	0.083
28	5.64	5.539	-0.017	6.58	7.273	0.106
29	6.06	6.164	0.017	7.27	7.639	0.050
31	5.69	5.552	-0.024	5.94	6.149	0.035
34	5.99	6.079	0.015	7.72	8.077	0.046
37	6.62	6.612	-0.001	8.97	8.527	-0.049
40	5.40	5.628	0.041	7.08	7.830	0.107