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

NIR Band Assignment of TanshinoneⅡA and Cryptotanshinone by 2D-COS Technology and Model Application Tanshinone Extract

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1600~1800,1900~2230和2300~2400 nm处有特征吸收,其中丹参酮ⅡA在1640和2140 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,1696 nm为丹参酮ⅡA和隐丹参酮分子中甲基伸缩振动二级倍频,1726和1740 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,2146和2220 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,2300~2400 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R^(2)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。

The near-infrared(NIR)band assignment of TanshinoneⅡA and Cryptotanshinone were performed by 2D-COS technique in deuterated chloroform.According to the two-dimensional synchronous slice spectra of TanshinoneⅡA and Cryptotanshinone,TanshinoneⅡA and Cryptotanshinone have characteristic absorption at 1600~1800,1900~2230,and 2300~2400 nm.TanshinoneⅡA has characteristic bands at 1640 and 2140 nm which connected with the first double-frequency and combination frequency of furan ring double bond.1696 nm was the second double-frequency of methyl stretching vibration in TanshinoneⅡA and Cryptotanshinone molecules,the absorption at 1726 and 1740 nm were the second double-frequency of TanshinoneⅡA and Cryptotanshinone which connected with cyclohexene methylene stretching vibration,2146 and 2220 nm were the combined frequency of TanshinoneⅡA and Cryptotanshinone which linked with benzene ring C-C and C-H stretching vibration,a series of peaks at 2300~2400 nm were the combination frequencies of stretching vibration and bending vibration of methyl in TanshinoneⅡA 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 R 2 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.