Magnetic nano graphene oxide as solid phase extraction adsorbent coupled with liquid chromatography to determine pseudoephedrine in urine samples
Introduction
Pseudoephedrine is a sympathomimetic amine classified as an amphetamine-type chemical known to affect the central nervous system and make patients feel excited and stimulated [1], [2], [3]. The growing consumption of pseudoephedrine may be related to its presence in various pharmaceutical dosage forms commonly used for the symptomatic treatment of the common cold, hypersensitivity, asthma, and spasms and for its diaphoretic and stimulant properties [4], [5]. Pseudoephedrine is widely applied in the manufacture of illicit synthetic drugs, such as methamphetamine, that have euphoric properties and a very high addiction risk. Therefore, the diversion of pseudoephedrine to synthetic drugs is of great concern. Pseudoephedrine is listed as an illegal drug that might be administered in doping and is prohibited by the Medical Commission of the International Olympic Committee (MCIOC). A concentration higher than the permitted limit for the presence of pseudoephedrine in urine results in a positive drug test for an athlete [6], [7]. Furthermore, pseudoephedrine is widely abused solely or in combination with other stimulant drugs, and that has led regulatory organizations to legislate restrictions for its production, distribution, and medical administration [8], [9], [10]. Quantitative analysis of drugs in human fluids is still a great challenge because of the complex matrix of biological fluids and demands for pretreatment and extraction prior to analysis. Common analytical extraction methods, such as liquid–liquid extraction (LLE), have been used to pretreat biological samples before analysis of many drugs [11], [12], but the application of LLE is limited because it is time-consuming and laborious. Solid phase extraction (SPE) has been developed because it is highly selective and sensitive and produces less toxic waste [13], [14], [15]. Magnetic solid phase extraction (MSPE) has been developed in recent years as a new sample preparation method [16]. Magnetic nanoparticles (MNPs) are composite materials that seem to affect extraction by having a high surface area-to-volume ratio. Moreover, the application of MNPs in sample preparation leads to faster separation after extraction in the presence of an external magnetic field compared with common SPE methods. Chemical oxidation of graphite powder results in graphene oxide (GO) sheets, a hydrophobic carbon material with good dispersion in aqueous media due to the presence of hydroxyl, carboxyl, and epoxy polar groups on its lamellar structure surface [17], [18]. Its high adsorption capacity introduces nano-GO as a novel adsorbent in SPE. The preparation of the nanomagnetic composite of GO may combine the high adsorption capacity of GO with the convenient separation of the target analyte in extraction by a magnetic field. Pseudoephedrine's chemical structure (Fig. 1) makes it a good candidate for MSPE extraction because of the presence of a benzene ring which provides a strong π–π interaction with MNGO. Moreover, the presence of hydroxyl and amine groups may offer a chance for a hydrogen bond and ionic interaction with active groups in MNGO. To the best of the authors' knowledge, there is no report on determining the presence of pseudoephedrine in biological matrixes by MSPE. In addition, the ability of MNGO to extract drug and its potential for application as a MSPE adsorbent may be interesting topics in analytical chemistry. In the present study, nano-GO was synthesized and functionalized by nanomagnetic particles. After MNGO synthesis, it was fully characterized and confirmed, then applied as an adsorbent for the extraction of pseudoephedrine from urine to determine and quantify it with high performance liquid chromatography equipped with an ultra violet detector (HPLC-UV).
Section snippets
Reagents and materials
Expanded graphite powder, KH2PO4, H2SO4 (98%), H2O2 (30%), KMNO4, FeCl2·4H2O, FeCl3·6H2O, KOH, NaOH, NH3 (25%), and HCl were purchased from Merck Chemicals (Darmstadt, Germany). Pseudoephedrine hydrochloride stock solution 1000 μg/mL in methanol was kindly donated by the Zahravi Pharmaceutical Co., (Tabriz, Iran). Acetonitrile, acetone, methanol, and dichloromethane (all in HPLC grade) were purchased from Duksan Co., Ltd., (Ansan, South Korea). Double distilled water was purchased from Shahid
Characterization of nano-GO and MNGO
Fig. 2 summarizes the characterization of GO and MNGO by various techniques. In Fig. 2a, FT-IR peaks at 3447 and 1231 cm−1 indicate stretching and bending bands of the OH group. The peak at 1704 cm−1 is associated with the stretching of the CO band of the carboxyl group. The peak at 1634 cm−1 indicates that the CC aromatic band could be assigned to the skeletal vibration of unoxidized graphitic domains. Deformation of the CO band was present at 1073 cm−1. The spectrum of MNGO differed from GO in
Conclusion
MSPE is introduced as an alternative method to the commonly applied LLE and SPE methods for determining the presence of pseudoephedrine in urine samples. In this study, MNGO was applied as a novel and sensitive adsorbent for extracting pseudoephedrine from urine. This method successfully determined the presence of pseudoephedrine in positive urine samples. High extraction efficiency was achieved, resulting in a low detection limit. Due to the commercial availability of nanographene oxide and Fe3
Acknowledgment
Drug Applied Research Center of Tabriz University of Medical Science is greatly appreciated for supporting the study.
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