| Second-order calibration and pattern recognition are two hotspots in chemometrics research.Analytical methods that combine them with high-order instruments can solve many difficult problems in complex systems.The second-order calibration method cleverly uses mathematical separation to replace or enhance physical/chemical separation,which can avoid or simplify tedious preprocessing,realizing simultaneous and rapid qualitative and qua ntitative analysis of multiple components in complex systems.Chemical pattern recognition can extract the effective information of the research object to the maximum extent from the massive data so as to discriminate.In this work,two analytical instruments(HPLC-DAD and EEMs)are combined with different second-order calibration methods to quickly identify and quantitative analyze active substances in drugs and cosmetics.The main research contents are as follows:Chapter 2: In order to rapidly conduct qualitative and quantitative analysis of two novel anti-hepatitis C virus drugs,daclatasvir(DAC)and ledipasvir(LED)in human fluids,an intelligent analysis method of ATLD algorithm combined with excitation-emission matrix(EEM)fluorescence was establis hed.This method has powerful mathematical separation capabilities that can replace or augment physical/chemical separations,allowing simultaneous qualitative and quantitative determination of analytes despite spectral overlap between target analytes and the presence of unknown interfering components in the matrix.The average recoveries of DAC and LED range from 98.35% to 109.95%,and the correlation coefficients of both were greater than 0.99.In addition,multiple figures of merit also reflect the high sensitivity,good selectivity and low detection limit of the proposed method.The proposed analysis strategy is simple,efficient and green,and is expected to provide a new idea for the rapid detection of clinical drugs.Chapter 3: A smart strategy of PARAFAC algorithm combined with EEMs was proposed for the detection of propyl gallate(PG)and hydroquinone(HQ)in three skin care products.Using the same calibration model,the spectral overlap and the unknown interferences of three matrix backgrounds in t he analytical system can be perfectly resolved in a relatively short period of time.The average recoveries of the two target analytes are 89.07-97.27%,and the correlation coefficient are all greater than 0.997.Multiple quality factor parameters also reflect the feasibility of the proposed method.Skin care products with different background substrates could be analyzed simultaneously under the same calibration model and got satisfactory results,which further shows that the established analytical method is not only green and simple,but also reliable and versatile.It is expected to provide a reference basis for the detection of prohibited additives in the skin care products.Chapter 4: In this work,a simple and effective strategy for the determination of 12 active compounds of atractylodes macrocephala koidz.(AM)was proposed by using HPLC-DAD combined with ATLD algorithm.Utilizing the "second-order advantage",three common problems in HPLC could be resolved,namely baseline drifts,peak overlaps,and unknown interferences.12 compounds were rapidly eluted within 12.5 minutes,and the average spike recoveries are 90.0-109.0%(Anhui,China),85.5-109.9%(Hunan,China),and 80.8-103.3%(Zhejiang,China),respectively.The figures of merit reflected the feasibility of the proposed method.Compared with the results of the traditional univariate calibration method based on HPLC-UV technique,the proposed strategy further verified the reliability and simplicity of the mathematical separation.On this basis,partial least squares-discriminant analysis(PLS-DA)was applied to discriminate 113 AM samples from different geographical origins,and variable importance in projection(VIP)was used to further screen the main differential components that affect the regional division of AM.A series of results show that the AM samples from the different geographical regions have obviously different clustering trends,this shows the reliability of the discriminant model.Overall,the strategy is expected to provide a scien tific basis for the modern research of medicinal materials,and it is also conducive to the clinical use and market supervision of AM. |
