NIR Band Assignment of Tanshinone ⅡA and Cryptotanshinone by
2D-COS Technology and Model Application Tanshinone Extract
PENG Yan-fang1, WANG Jun1, WU Zhi-sheng2*, LIU Xiao-na3, QIAO Yan-jiang2*
1. Pharmacy Faculty, Hubei University of Chinese Medicine, Wuhan 430065, China
2. School of Chinese Materia, Beijing University of Chinese Medicine, Beijing 100029, China
3. College of Integrated Traditional Chinese Medicine and Wastern Medicine, Binzhou Medical University, Yantai 264003, China
摘要： 采用二维相关光谱（2D-COS）技术，以氘代氯仿为溶剂，解析了丹参酮ⅡA和隐丹参酮标准品的近红外光谱（NIR）。丹参酮ⅡA和隐丹参酮二维相关切片谱在1 600~1 800，1 900~2 230和2 300~2 400 nm处有特征吸收，其中丹参酮ⅡA在1 640和2 140 nm处有不同于隐丹参酮的呋喃环双键一级倍频和组合频吸收，1 696 nm为丹参酮ⅡA和隐丹参酮分子中甲基伸缩振动二级倍频，1 726和1 740 nm处吸收为丹参酮ⅡA和隐丹参酮环己烯亚甲基伸缩振动二级倍频，2 146和2 220 nm为丹参酮ⅡA和隐丹参酮苯环C—C伸缩振动与C—H伸缩振动的组合频，2 300～2 400 nm处一系列峰为丹参酮ⅡA和隐丹参酮甲基伸缩振动与弯曲振动组合频吸收。以丹参酮提取物为载体，以丹参酮ⅡA和隐丹参酮光谱解析特征波段及组合间隔偏最小二乘（SiPLS）筛选特征波段分别建立偏最小二乘（PLS）定量模型，模型的决定系数R2均大于0.9，校正均方根误差（root mean of square error of calibration, RMSEC）和交叉验证均方根误差（RMSECV），预测均方根误差（RMSEP）均较小。结果表明，2D-COS技术解析特征波段与SiPLS波段筛选所建PLS模型均稳定。2D-COS技术使近红外定量模型更具解释性，可解析出结构差异特征吸收，同一波段可实现结构类似物的同时定量测定。
关键词：丹参酮ⅡA；隐丹参酮；近红外光谱；二维相关光谱；丹参酮提取物；光谱解析
Abstract：The near-infrared (NIR) band assignment of Tanshinone ⅡA and Cryptotanshinone were performed by 2D-COS technique in deuterated chloroform. According to the two-dimensional synchronous slice spectra of Tanshinone ⅡA and Cryptotanshinone, Tanshinone ⅡA and Cryptotanshinone have characteristic absorption at 1 600~1 800, 1 900~2 230, and 2 300~2 400 nm. Tanshinone ⅡA has characteristic bands at 1 640 and 2 140 nm which connected with the first double-frequency and combination frequency of furan ring double bond. 1 696 nm was the second double-frequency of methyl stretching vibration in Tanshinone ⅡA and Cryptotanshinone molecules, the absorption at 1 726 and 1 740 nm were the second double-frequency of Tanshinone ⅡA and Cryptotanshinone which connected with cyclohexene methylene stretching vibration, 2 146 and 2 220 nm were the combined frequency of Tanshinone ⅡA and Cryptotanshinone which linked with benzene ring C—C and C—H stretching vibration, a series of peaks at 2 300~2 400 nm were the combination frequencies of stretching vibration and bending vibration of methyl in Tanshinone ⅡA and Cryptotanshinone molecules. Taking Tanshinone Extract as a carrier, the characteristic band by 2D-COS and the band by synergy interval Partial Least Squares (SiPLS) were used to establish Partial Least Square (PLS) quantitative models. The coefficients of determination R2 were all greater than 0.9, the Root Mean of Square Error of Calibration (RMSEC) and Root Mean of Square Error of Cross-Validation (RMSECV), and the Root Mean of Square Error of Prediction (RMSEP) were very small. The results showed that the PLS model established by 2D-COS and SiPLS were both good. The quantitative model based on the 2D-COS technique was explanatory. 2D-COS can be used to analyze the characteristic absorption connected with a structural differences. The simultaneous quantitative determination of structural analogues can be realized in the same band.
彭严芳，王 君，吴志生，刘晓娜，乔延江. 丹参酮ⅡA和隐丹参酮近红外光谱的2D-COS解析及其在丹参酮提取物近红外模型中应用[J]. 光谱学与光谱分析, 2022, 42(06): 1781-1785.
PENG Yan-fang, WANG Jun, WU Zhi-sheng, LIU Xiao-na, QIAO Yan-jiang. NIR Band Assignment of Tanshinone ⅡA and Cryptotanshinone by
2D-COS Technology and Model Application Tanshinone Extract. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(06): 1781-1785.
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