可待因及福尔可定的密度泛函理论计算模拟和表面增强拉曼光谱测定  

Density Functional Theory Simulation and Surface-Enhanced Raman Spectrometric Determination of Codeine and Falcodine

作　　者：吴国萍[1,2] 胡辰辰 陆腾 吴元钊 WU Guoping;HU Chenchen;LU Teng;WU Yuanzhao(Department of Criminal Science and Technology,Jiangsu Police Institute,Nanjing 210031,China;Jiangsu Provincial Engineering Laboratory for Technical and Criminal Inspection of food,Drug and Environmental Cases,Nanjing 210031,China;Department of High Performance Computing Technology and Application Development,Computer Network Information Center,Chinese Academy of Sciences,Beijng 100049,China;Key Laboratory of Drug Prevention and Control Technology of Zhejiang Province,Department of Criminal Science and Technology,Zhejiang Police College,Hangzhou 310051,China)

机构地区：[1]江苏警官学院刑事科学技术系,南京210031 [2]江苏省食品药品与环境犯罪检验技术工程实验室,南京210031 [3]中国科学院计算机网络信息中心高性能计算技术与应用发展部,北京100049 [4]浙江警官学院刑事技术系,浙江省毒品防控技术研究重点实验室,杭州310051

出　　处：《理化检验（化学分册）》2022年第3期256-263,共8页Physical Testing and Chemical Analysis(Part B:Chemical Analysis)

基　　金：浙江省毒品防控技术研究重点实验室开放课题(2019001);江苏省教育厅自然科学重大项目(18KJA620001);公安部公安理论及软科学计划(2021LL21)。

摘　　要：运用密度泛函理论(DFT)对可待因及福尔可定进行几何构型优化,从而对标准品粉末的拉曼光谱的振动模式进行指认和归属,并与低浓度水平标准溶液的表面增强拉曼谱图进行比较。进一步优化了表面增强拉曼光谱检测条件,并摸索可待因及福尔可定的测定下限及定量分析的可行性。结果表明,可待因及福尔可定大部分特征峰拉曼位移的理论计算值、拉曼光谱测定值、表面增强拉曼光谱测定值是一致的,但会有一定程度的蓝移和红移;可待因、福尔可定的测定下限均为10 mg·L^(-1)。可待因在631.29 cm^(-1)和1 595.26 cm^(-1)处、福尔可定在628.58 cm^(-1)和1 251.41 cm^(-1)处的特征峰强度比值,与其对应的质量浓度(40~100 mg·L^(-1))呈线性关系。对空白基质进行加标回收试验,可待因和福尔可定的回收率分别为99.0%~105%和102%~104%,测定值的相对标准偏差(n=5)分别为5.3%,5.9%。上述方法可为这两种管制药品提供拉曼光谱检测的理论依据和快检支持。Density functional theory(DFT) was used to optimize the geometric configurations of codeine and falcodine, so as to identify and assign the vibration modes of the Raman spectra of the standard powder, and Raman spectra of standard powder was compared with the surface-enhanced Raman spectra of standard solution at low concentration levels. The detection conditions of surface-enhanced Raman spectroscopy were further optimized, and the lower limits of determination and the feasibility of quantitative analysis of codeine and falcodine were discussed. As shown by the results, the theoretical values and detection values by Raman spectra and surface-enhanced Raman spectra were basically consistent for Raman shifts of most characteristic peaks of codeine and fordrine, while there would be a certain degree of blue shift and red shift. Lower limits of determination of codeine and fordrine were both 10 mg·L^(-1). Linear relationships between mass concentration and characteristic peak intensity ratio(codeine at 631.29 cm^(-1)and 1 595.26 cm^(-1)and fordrine at 628.58 cm^(-1)and 1 251.41 cm^(-1)) were kept in the same range of 40-100 mg·L^(-1). Test for recovery was made on blank matrix by standard addition method, giving results in the range of 99.0%-105% for codeine and 102%-104% for fordrine, with RSDs(n=5) of the determined values of 5.3% and 5.9%, respectively. The above methods could provide theoretical basis and rapid detection support for the two controlled drugs.

关 键 词：密度泛函理论 表面增强拉曼光谱 可待因 福尔可定 

分 类 号：O657.37[理学—分析化学]