基于非接触式拉曼光谱分析人血与犬血的PCA-LDA鉴别方法

doi:10.7503/cjcu20160676

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (4): 575.doi: 10.7503/cjcu20160676

基于非接触式拉曼光谱分析人血与犬血的PCA-LDA鉴别方法

郑祥权^1,², 廖鑫^1,², 徐溢^1,^2,³(), 洪明坚^1,⁴()

1. 重庆大学新型微纳器件与系统技术重点学科实验室
2. 化学化工学院
3. 光电工程学院微系统研究中心
4. 软件学院, 重庆 400030

收稿日期:2016-09-23 出版日期:2017-04-10 发布日期:2017-03-16
作者简介:联系人简介: 徐溢, 女, 博士, 教授, 博士生导师, 主要从事分析化学、应用化学和微型集成生化分析系统等方面的研究. ; E-mail: xuyibbd@sina.com;洪明坚, 男, 博士, 副教授, 主要从事光谱分析模式识别等方面的研究. E-mail: hmj@cqu.edu.cn
基金资助:
国家自然科学基金(批准号: 21375156)、重庆市科委基础科学与前沿技术重点项目(批准号: cstc2015jcyjBX0010)和国家“八六三”计划项目(批准号: 2015AA021104)资助

PCA-LDA Analysis of Human and Canine Blood Based on Non-contact Raman Spectroscopy^†

ZHENG Xiangquan^1,², LIAO Xin^1,², XU Yi^1,^2,^3,^*(), HONG Mingjian^1,^4,^*()

1. Key Disciplines Lab of Novel Micronano Devices and System Technology
2. School of Chemistry and Chemical Engineering
3. School of Optoelectronics Engineering, Research Center of Microsystems
4. School of Software, Chongqing University, Chongqing 400030, China

Received:2016-09-23 Online:2017-04-10 Published:2017-03-16
Contact: XU Yi,HONG Mingjian E-mail:xuyibbd@sina.com;hmj@cqu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21375156), the Frontier Research Key Projects of Chongqing Science and Technology Committee, China(No cstc2015jcyjBX0010) and the National High Technology Research and Development Program of China(No.2015AA021104)

摘要/Abstract

摘要：

将拉曼光谱分析法与数理统计方法有机结合, 构建人血与犬血种属判别模型, 实现了不同种属血液样本的高效无损鉴别. 采用拉曼光谱的无损测试模式对血液样本进行测试, 考察了抗凝管管材、聚焦位置及曝光时间等对血液样本拉曼光谱的影响, 在激发波长为632.8 nm, 光谱扫描范围为200~1800 cm^-1, 功率衰减率50%, 曝光时间5 s及累加次数为2次的优化条件下, 获得了无损检测条件下的血液样本拉曼光谱图. 针对血液样本组分复杂、拉曼光谱信号基底背景高等问题, 提出了基于小波变换去噪, 进行分段多项式基线校正的预处理方法, 有效解决了血液样本拉曼光谱谱图的高噪音和基线漂移问题. 实验选择30例正常人血和33例比格犬血为样本训练集, 5例正常人血和5例比格犬血为测试集, 基于主成分分析法(PCA)联合线性判别法(LDA)模型, 训练集分类正确率达到95.23%, 盲测集分类正确率达90.00%. 这种基于非接触式血液样本拉曼光谱和PCA-LDA判断模型的测试方法在进出口检验检疫等涉及血液无损鉴别的领域具有广泛的应用价值和前景.

关键词: 人血, 犬血, 非接触式拉曼光谱测试, 主成分分析法-线性判别法

Abstract:

Efficient and rapid non-destructive screening method for human and animal blood has great significance and practical prospects in export inspection and quarantine, forensic testing and other areas. By taking full advantages of Raman spectroscopy and combination of mathematical and statistical methods, species discriminant model for human blood and canine blood was established in this paper. First of all, the non-destructive Raman spectroscopy test for blood samples was focused. The factors which affected the non-destructive test were investigated in details, such as the material of anticoagulant tubes, the focus position and exposure time in Raman detecting and so on. Raman spectra of human and canine blood samples were obtained under the optimal conditions. The effective spectra were accumulated with 633 nm excitation in spectral range of 200—1800 cm^-1 with a 5 s integration time and 2 accumulating times. Laser power was selected approximately 8.85 mW. In view of the complexity of the blood sample composition and the high signal background of the Raman spectrum, the pretreatment method of wavelet denoising and piecewise polynomial baseline correction for the series of Raman spectra was proposed and solved effectively the recognition rate of the Raman spectrum. The model of multivariate statistical algorithm was established from the training data which set consisted of 30 spectra from human blood and 33 spectra from dog blood and the testing data which included five spectra from human blood and five spectra from dog blood by combining principal component analysis(PCA) with linear discriminant analysis(LDA) in MATLAB to identified the species of human and dog blood. The classification accuracy of proposed model for the calibration set and the blind test are 95.23% and 90.00%. Studies have shown that based on the non-contact method of testing blood samples Raman and PCA-LDA classification model has broad application value and prospect in the fields of import and export inspection and quarantine blood nondestructive identification.

Key words: Human blood, Canine blood, Non-destructive test of Raman spectroscopy, Principal component analysis(PCA)-linear discriminant analysis(LDA)

中图分类号:

O657.37

TrendMD:

郑祥权, 廖鑫, 徐溢, 洪明坚. 基于非接触式拉曼光谱分析人血与犬血的PCA-LDA鉴别方法. 高等学校化学学报, 2017, 38(4): 575.

ZHENG Xiangquan, LIAO Xin, XU Yi, HONG Mingjian. PCA-LDA Analysis of Human and Canine Blood Based on Non-contact Raman Spectroscopy^†. Chem. J. Chinese Universities, 2017, 38(4): 575.

图/表 12

Fig.1 Raman spectrum of human blood in the range of 200—4000 cm-1

Fig.2 Raman spectrum of glass anticoagulant tubes

Fig.3 Raman spectra of human blood at attenuation power of 10%(A), 25%(B), 50%(C) and 75%(D)

Fig.4 Raman spectra of human blood at focus position of 0(A), 0.5 mm(B), 1 mm(C) and 1.4 mm(D)

Fig.5 Raman spectra of canine(a) and human blood(b) by testing on glass substrate(A) and non-destructive testing in tube(B)

Fig.6 Raman spectra of human blood after pretreatment

Fig.7 Scores plot for Raman spectra of human and canine blood

Fig.8 Loading plot of PC1(A) and PC2(B)

Table 1 Raman spectral peaks of human and canine blood by non-destructive testing in the tube and on the glass substrate

Sample	State	Peak/cm^-1
Human blood	Outside	673	752	975	999	1122	1172	1223	1546	1561	1615	1637
Canine blood	Outside	673	752	977	1000	1122	1169	1223	1547	1561	1618	1634
Human blood	Non-destructive		755					1223	1546	1564		1637
Canine blood	Non-destructive		755					1223	1545	1562		1636

Table 2 Typical characteristic peaks of human and canine blood[10,24,25]

Characteristic peak/cm^-1		Vibrational mode
PC1		PC2
	743
753	754	752(T)
1222	1222	Protein
	1340	A, Tryptophan, γCH₂
1549		Phenylalanine, deoxyribose, A, U, C
	1559
1563		Heme
1618		Heme
1637	1638	A

Fig.9 Scores plot for Raman spectra of unknown samples

Table 3 PCA scores plots for matrix M and the result of prediction

Unknown sample	PC1	PC2	Actual identity	Predicted class
1	-145.78	-42.36	Canine	Canine
2	-77.81	125.12	Human	Human
3	-52.07	-61.80	Canine	Canine
4	-74.59	-31.02	Canine	Human
5	-93.47	47.68	Human	Human
6	214.96	145.77	Human	Human
7	-13.74	-21.95	Canine	Human
8	-145.66	-44.83	Canine	Canine
9	-234.56	-7.00	Human	Canine
10	-122.37	-45.01	Canine	Canine
Correct rate	90.00%

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基于非接触式拉曼光谱分析人血与犬血的PCA-LDA鉴别方法

PCA-LDA Analysis of Human and Canine Blood Based on Non-contact Raman Spectroscopy^†

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基于非接触式拉曼光谱分析人血与犬血的PCA-LDA鉴别方法

PCA-LDA Analysis of Human and Canine Blood Based on Non-contact Raman Spectroscopy†

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PCA-LDA Analysis of Human and Canine Blood Based on Non-contact Raman Spectroscopy^†