Spectrophotometric determination of fluoxetine by molecularly imprinted polypyrrole and optimization by experimental design, artificial neural network and genetic algorithm

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Highlights

  • A selective method based on solid-phase extraction (SPE) was developed.

  • A molecularly imprinted polypyrrole for fluoxetine was prepared.

  • UV–Vis spectrophotometry as a detection technique was applied.

  • PBD, CCD, GA were performed for optimization of parameters.

  • Fluoxetine in pharmaceutical and biological samples was determined.

Abstract

A selective method based on molecularly imprinted polymer (MIP) solid-phase extraction (SPE) using UV–Vis spectrophotometry as a detection technique was developed for the determination of fluoxetine (FLU) in pharmaceutical and human serum samples. The MIPs were synthesized using pyrrole as a functional monomer in the presence of FLU as a template molecule. The factors that affecting the preparation and extraction ability of MIP such as amount of sorbent, initiator concentration, the amount of monomer to template ratio, uptake shaking rate, uptake time, washing buffer pH, take shaking rate, Taking time and polymerization time were considered for optimization. First a Plackett–Burman design (PBD) consists of 12 randomized runs were applied to determine the influence of each factor. The other optimization processes were performed using central composite design (CCD), artificial neural network (ANN) and genetic algorithm (GA). At optimal condition the calibration curve showed linearity over a concentration range of 10 7–10 8 M with a correlation coefficient (R2) of 0.9970. The limit of detection (LOD) for FLU was obtained 6.56 × 10 9 M. The repeatability of the method was obtained 1.61%. The synthesized MIP sorbent showed a good selectivity and sensitivity toward FLU. The MIP/SPE method was used for the determination of FLU in pharmaceutical, serum and plasma samples, successfully.

Introduction

The selective serotonin reuptake inhibitor (SSRI) FLU is widely used to treat depression, obsessive compulsive disorder, bulimia, and panic disorder [1]. FLU (Scheme 1) is a phenyltolylpropylamine also known as prozac and presents a high selectivity for the 5-hydroxytryptamine (5-HT) transporter, thus modulating the concentration of serotonin in the synapses [2]. The methods described for analysis of FLU are consist of ultra performance liquid chromatography tandem mass spectrometry (UPLC–MS/MS) [3], two-dimensional liquid chromatography system coupled to triple quadrupole tandem mass spectrometer (2D LC–MS/MS) [4], liquid chromatography with fluorescence and diode array detection [5], [6], differential pulse voltammetry [7] and UV spectrophotometric method [8]. Among the mentioned detection methods, UV spectrophotometry is not time consuming and is more cost effective comparing the other methods.

SPE is a widely used sample-preparation technique for the isolation of selected analytes, usually from a mobile phase (gas, fluid or liquid) [9]. The flexibility and through-put of SPE has facilitated applications in many different fields such as; environmental, drug analysis, proteomics and DNA analysis for a multitude of purposes e.g., purification, enrichment, desalting and fractionation [10]. In addition, useful aims of SPE are trace concentration, matrix simplification and medium exchange [9].

MIPs are synthetic polymers with specific cavities designed for a target molecule and based on the key-lock model. They have been largely applied as SPE sorbents to selectively extract target analytes from complex matrixes [11]. MIP has the advantages of low cost to produce, stability and robustness and resistance to a wide range of pH, solvents, and temperature [12]. In particular, MIPs used as adsorbents of SPE are widely involved in the concentration and enrichment of drug molecules, and the extraction of active components from complex natural matrixes [13]. Among the convenient polymerization methods such as bulk polymerization, precipitation polymerization, suspension polymerization, sol–gel polymerization that have been reported for the synthesis of MIPs [14], precipitation polymerization is an easy and cost effective process for this purpose [14].

Design of experiments refers to the process of planning, designing and analysing the experiment so that valid and objective conclusions can be drawn effectively and efficiently [15]. PBD allow the experimenters to evaluate a large number of process/design parameters in a minimum number of trials [15]. Response surface methodology (RSM) and ANN are modeling tools able to solve linear and non-linear multivariate regression problems [16]. ANN, is a data processing system consisting of a large number of simple, highly interconnected processing elements in an architecture inspired by the structure of the brain [17].

GA is a global search and optimization method that mimics natural biological evolution [18]. GA is based on the principles of evolution through natural selection, that is, the survival of the fittest strategy [19].

In this work, CCD, ANN and GA were used to design the experiments, modeling and optimization, respectively. To the best of our knowledge there is no report of determination of FLU using molecularly imprinted polymer with UV–Vis detection.

Section snippets

Materials

FLU was prepared from Sajad Daru pharmaceutical company (Mashhad, Iran). Stock solution of FLU (1 × 10 2 M) was prepared in methanol. The standard solutions were prepared by diluting the stock solution of FLU using methanol. Pyrrole, ethanol, methanol, ammonia and copper (II) chloride were purchased from Merck. Simvastatin, famotidine, ketorolac, rabeprazole and celecoxib were received from Sajad Daru pharmaceutical company. Fexofenadine was obtained from Samisaz pharmaceutical company (Mashhad,

Experimental Design

According to the preliminary experiments, the factors, i.e. amount of sorbent (AS), initiator concentration (INC), the amount of monomer to template ratio (MTR), uptake shaking rate (SHU), Uptake time (UT), washing buffer pH (pH), take shaking rate (SHT), taking time (TT), polymerization time (PT) were expected to influence preparation and extraction ability of MIP. As a screening method approaches such as factorial or PBD involve seeing which factors are important for the success of a process

Conclusion

Spectrophotometric determination of FLU after selective extraction by MIP was studied. The MIP was synthesized by precipitation polymerization of pyrrole. The Parameters which were expected to control the performance of MIP, i.e. AS, INC, MTR, SHU, UT, pH, SHT,TT and PT were optimized. The optimization process was performed using PBD, CCD, ANN and GA. Optimization using CCD as the experimental design, ANN as the modeling tool based on the CCD and GA as an optimization algorithm based on the CCD

Acknowledgements

The authors acknowledge Payame Noor University (PNU) (grant number 1/12/68) Research Council for financial support of this work.

References (27)

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