Comparative study of partial least squares and multivariate curve resolution for simultaneous spectrophotometric determination of pharmaceuticals in environmental samples

Abstract

25 The potential of partial least squares regression (PLSR) and multivariate curve resolution 26 alternating least squares (MCR-ALS) is evaluated for simultaneous determination of 27 diclofenac (DCF), naproxen (NAP), mefenamic acid (MEF) and carbamazepine (CBZ) 28 as target analytes and gemfibrozil (GEM) as interference in synthetic and real 29 environmental samples. The analysis of first-order UV-Vis spectra is performed using 30 PLSR with different variable selection methods including variable importance in 31 projection (VIP), recursive partial least squares (rPLS), regression coefficient (RV) and 32 uninformative variable elimination (UVE) and using MCR-ALS with correlation 33 constraint (MCR-ALS-CC). The obtained statistical parameters in terms of relative error 34 (RE), regression coefficient (R 2 ) and root mean square error (RMSE) were satisfactory 35 for calibration and validation sets. Furthermore, in real environmental samples, the 36 obtained statistical parameters of PLSR using VIP and rPLS and also MCR-ALS-CC 37 were reasonable by considering the heavy overlap of target analytes and complex 38 samples matrices. In general, PLSR showed better performance for determination of 39 analytes in samples which are free of interference or contains calibrated interference(s). 40On the other hand, MCR-ALS-CC allowed for the accurate determination of analytes in 41 the presence of unknown interference and more complex sample matrices. 42

Simultaneous Determination of Drugs Affecting Central Nervous System (CNS) in Bulk and Pharmaceutical Formulations Using Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS)

“…is study established a spectrophotometric method using MCR-ALS for simultaneous determination of imipramine, carbamazepine, chlorpromazine, haloperidol, and phenytoin in commercial formulations. An overview of analytical methods reported for the determination of CNS affecting drugs in pharmaceutical dosage forms revealed that all reported methods [6][7][8][9][10][11] either use or generate harmful solvents. Moreover, LODs of the proposed method were similar to or even better than those of the reported methods.…”

“…Several methods have been developed for the analysis of these drugs, either individually or in combination. For example, partial least squares (PLS) and MCR-ALS were used for the simultaneous determination of carbamazepine along with diclofenac, naproxen, and other anti-inflammatory drugs [6]. HPLC-DAD was used for the analysis of carbamazepine and phenobarbital in human serum samples and was further evaluated by the MCR-ALS method [7].…”

Simultaneous Determination of Over-the-Counter Pain Relievers in Commercial Pharmaceutical Products Utilizing Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) Multivariate Calibration Model

“…Compared to chromatographic methods that utilize sophisticated instruments and consume or generate large volumes of organic solvents, spectrophotometric methods are faster, more economical, and greener, making them fully functional alternatives. However, spectrophotometric techniques suffer from lack of selectivity especially in case of severe spectral overlap and matrix interferences, the selectivity of such techniques can be enhanced by using multivariate calibration models [8, 9]. The development of multivariate calibration methods such as multivariate curve resolution-alternating least squares (MCR-ALS) (based on signals mathematical resolution) enables the resolution and quantification of strongly overlapped spectra of multicomponent samples [10].…”

“…MCR-ALS has recently attracted attention in the analytical chemistry society and has been shown to provide enhanced resolution and improved quantitative determination of different analytes in samples of increasing complexity such as environmental matrices [11] and pharmaceutical and agricultural samples [10, 12]. The main advantage of using MCR-ALS is the possible recovery of the spectral information of target analytes and unknown interferences [9]. Different analytical methods have been developed for the individual assay of the OTC pain relievers and also for some of their combinations including HPLC (e.g.…”

Least Absolute Shrinkage and Selection Operator as a Multivariate Calibration Tool for Simultaneous Determination of Diphenylamine and its Nitro Derivatives in Propellants

“…When one uses first order data (e. g., UV-Vis spectra) the appearance of overlapping spectra and matrix effects may reduce the accuracy and precision of the analysis. Multivariate calibration methods have been proposed to overcome fundamental mathematical challenges occurred during analysis of these types of data [12]. Among different multivariate calibration techniques, projection-based methods such as principal component regression (PCR) and partial least squares (PLS) have attracted attention in recent years and these methods have been used for determination of different analytes in various types of matrices [13][14][15][16][17][18][19][20][21][22].…”