Elsevier

Biosensors and Bioelectronics

Volume 101, 15 March 2018, Pages 90-95
Biosensors and Bioelectronics

3D spongy graphene-modified screen-printed sensors for the voltammetric determination of the narcotic drug codeine

https://doi.org/10.1016/j.bios.2017.10.020Get rights and content

Highlights

  • 3D spongy graphene modified screen-printed sensors were fabricated via a green route.

  • Adenine-functionalized graphene is a promising sensing material for pharmaceutical formulations.

  • The sensor showed a wide linear response range of 2.0 × 10−8–2.0 × 10−4 M.

  • The sensor showed a detection limit of 5.8 × 10−9 M towards the sensing of codeine.

Abstract

Adenine-functionalized spongy graphene (FSG) composite, fabricated via a facile and green synthetic method, has been explored as a potential electrocatalyst toward the electroanalytical sensing of codeine phosphate (COD). The synthesized composite is characterized using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray powder diffraction, UV−vis absorption spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy (HRTEM), and thermogravimetric analysis. The FSG was electrically wired via modification upon screen-printed (macro electrode) sensors, which behave as a hybrid electrode material for the sensitive and selective codeine phosphate (COD) determination in the presence of paracetamol (PAR) and caffeine (CAF). The FSG- modified sensor showed an excellent electrocatalytic response towards the sensing of COD with a wide linear response range of 2.0 × 10−8–2.0 × 10−4 M and a detection limit (LOD) of 5.8 × 10−9 M, indicating its potential for the sensing of COD in clinical samples and pharmaceutical formulations.

Introduction

Codeine (methyl morphine, COD) is a natural opiates alkaloid naturally found in the poppy plant (Thorn et al., 2009), which is widely used as powerful antitussive and analgesic agent (Chen et al., 1991). Nevertheless, long-term use of COD is addictive and extreme intake can even cause death (Häkkinen et al., 2012). Thus, the World Health Organization (WHO), the US Food and Drug Administration (FDA), and the European Medicines Agency (EMA), among many other international organizations, have recently issued strict warnings concerning the adverse effects of COD (Tobias et al., 2016). In particular, COD has a recognized abuse liability due to its effect and progress of tolerance within a little timeframe on regular or excessive use (Van Hout and Norman, 2016). Also, smoking centrally activates the transformation of codeine to morphine, which may cause COD addiction in the brain (Niaz et al., 2016). Therefore, the need to monitor and detect COD using simple, fast, and reliable protocols is of paramount importance. Several analytical methods based on electrochemical techniques have been reported for the determination of COD (Afkhami et al., 2014a, Babaei et al., 2012, Bagheri et al., 2016, Batista Deroco et al., 2015, Ensafi et al., 2015, Habibi et al., 2014, Mashadizadeh et al., 2016, Pournaghi‐Azar and Saadatirad, 2010, Santos et al., 2015; Silva et al., 2017).

On the other hand, paracetamol (PAR) is commonly used in combination with other drugs, such as codeine and caffeine. PAR is an efficient narcotic used for the release of pain related with several parts of the human body (http://en.wikipedia.org/wiki/Paracetamol). When taken in normal therapeutic doses, PAR has no significant toxic side effects on public health (Martin and McLean, 1998). However, skin rashes, liver disorders, nephrotoxicity and inflammation of the pancreas are the usual side effects seen upon the use of excess doses and chronic use of PAR (Martin and McLean, 1998). Thus, precise determination and control of its quality is vital. Moreover, caffeine (CAF) is a natural alkaloid stimulant found in different commercial products, such as beverages, energy drinks, food supplements, and medicinal preparations, among others (Peacock et al., 2013). Often, CAF is added to analgesic pharmaceutical preparations because of its diuretic action (Lourencao et al., 2009).

Due to the importance of the above-mentioned drugs and their extensive global use, their identification and measurement within human body fluids is a relevant analytical challenge. Earlier simultaneous determination of these drugs have been reported using chromatographic methods (Kartal, 2001). However, those methods require high cost apparatus, trained labor, and complex working routines involving different analytical steps. In this regard, electroanalytical methods overawed these disadvantages and offer similar or better analytical information than those achieved from the use of chromatographic methods.

Today, considerations have been devoted to the use of nanomaterials as integrated components of the biosensing technology for the detection of opiate drugs such as codeine. Biosensing protocols have shown suitable results for environmental control, toxicity detection, and food quality screening (Bagheri et al., 2017b, Gheibi et al., 2015, Mohamed et al., 2017a, Mohamed et al., 2017b). To this end, graphene-based materials have been explored as effective sensing materials due to their high specific surface area, excellent chemical stability, mechanical and electrical properties, and the achievability for mass production of chemically-modified graphene (CMGs) sensors (Bagheri et al., 2015a, Bagheri et al., 2015b, Bagheri et al., 2015c, Bagheri et al., 2017a). However, the synthesis of graphene using conventional reducing agents (e.g., hydrazine, dimethyl hydrazine, and NaBH4) is unsafe and the resulted graphene has a strong propensity to restack due to the π –π interactions (Dubin et al., 2010; Hassanien et al., 2016; Park and Ruoff, 2009; Zhu et al., 2010). Therefore, a simple, eco-friendly method to produce graphene is critically needed.

Herein, a simple method is utilized to fabricate functionalized spongy graphene (FSG) through freeze-drying a graphene oxide solution in the presence of adenine, which inhibits graphene sheets from restacking, resulting in a 3D interconnected and permeable arrangement. Such a 3D arranged structure gives rise to exposed edge plane sites/defects allowing optimal charge transfer/electrode kinetics. This was trailed by functionalisation of the spongy graphene oxide with adenine. The interaction between the host materials can be evidenced from the involved functional groups, resulting in several changes of the structure of graphene that are expanding the interlayer spacing or layer scrolling. Say it was reduced to graphene After annealing, a functionalized spongy graphene architecture (FSG) is obtained which helps to avoid the stacking between graphene interlayers and reduce the likelihood of forming graphite. It is worth mentioning that FSG has not previously been explored towards the electrochemical detection/sensing of COD. The use of FSG-modified screen-printed electrodes (SPEs) improves the electrochemical response, compared to unmodified graphite SPEs, by decreasing the electrochemical oxidation potential of COD.

Specifically, we explore, for the first time, the utilisation of FSG as a potential sensing platform towards the detection of COD when immobilised on SPEs assembled as a sensor. The FSG-modified SPEs were also tested for the simultaneous determination of COD, PAR and CAF and compared to those reported in literature. FSG has not previously been reported as a beneficial electrocatalytic material when immobilised upon carbon or any other platforms applied towards the electrochemical detection of COD and in the presence of PAR and CAF.

Section snippets

Preparation of functionalized spongy graphene oxide (FSGO) and functionalized spongy graphene (FSG)

Spongy graphene oxide (SGO) was prepared from natural graphite using a modified Hummer's method (Park and Ruoff, 2009) of which details were labeled elsewhere followed by drying with a freeze-dryer to remove the water at a temperature of − 53 °C and a pressure of 10 Pa for 3 days (Park and Ruoff, 2009, Xu et al., 2015). The functionalized spongy graphene oxide was prepared by dispersing 0.1 g graphene oxide (GO) in distilled water (10 mL), then (0.3 g) adenine and equimolar amount of NaOH in

Morphological and structural characterization

Fig. 1a shows an FESEM image of the fabricated SGO surface, indicating a substantial increase in the thickness of the layers, which can be related to the formation of oxygen groups in the basal plane of graphene oxide. Upon adding adenine, Fig. 1b, the functionalized spongy graphene oxide (FSGO) becomes exfoliated with further increase in volume, resulting in the formation of flakes with wrinkled edges and crumbled sheets. The synthesized FSG, Fig. 1c, exhibits an interconnected and porous 3D

Conclusions

The electrocatalytic sensing of COD using adenine-functionalized spongy graphene (FSG) was demonstrated. The developed sensor exhibits low limits of detection (5.80 × 10−9 M) and quantification (1.93 × 10−8 M) with a wide linear range (2.00 × 10−8–2.00 × 10−4 M), introducing a promising alternative for the quantitative determination of PAR, COD and CAF in their mixtures as commonly found in pharmaceutical formulations. Compared to other analytical, the developed sensor is fast, potentially

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