Elsevier

Talanta

Volume 198, 1 June 2019, Pages 447-456
Talanta

Electrochemical determination of antihypertensive drugs by employing costless and portable unmodified screen-printed electrodes

https://doi.org/10.1016/j.talanta.2019.01.117Get rights and content

Highlights

  • Voltammetric determination antihyperteinsive drugs using SPEs in presence of SDS was explored.

  • LOD was found to be 0.0056, 0.042, 0.18, 0.0107 and 0.006 µM for PRO, TIM, AMI, TRI and AML drugs, respectively.

  • SPEs utilized for determination of antihyperteinsive drugs in pharmaceutical and urine samples.

Abstract

Hypertension increases the risk of heart disease and stroke, is commonly known as a silent killer disease and considered as one of the key risk factor for premature death and disability over the world. Herein, we report for the first time a sensitive, costless and reproducible voltammetric method for individual determination of five antihypertensive drugs namely, propranolol (PRO), timolol (TIM), amlodipine (AML), amiloride (AMI) and triamterene (TRI) using differential pulse voltammetry at bare/unmodified screen-printed carbon electrodes (SPEs) in presence of sodium dodecyl sulfate (SDS). Each drug exhibits an electrochemical signal in aqueous media which is significantly enhanced in presence of optimized concentration of SDS due to accumulation of the protonated drug molecules and electrostatically interaction with negatively charged micellar structures. As a result, the spherical micellar orientation of SDS onto the graphitic surface of SPEs offered the analytically sensitive determination of the target drugs over a wide linear concentration range with nano-molar detection limits possible negating the need for any complicated surface modifications. Finally, the proposed voltammetric method was successfully utilized in the individual determination of the target antihypertensive drugs in pharmaceutical formulations and human urine samples.

Graphical abstract

Electrochemical analyses of antihypertensive drugs (propranolol, timolol, amlodipine, amiloride and triamterene) were explored by employing unmodified screen-printed electrode (SPE) in micellar media. The SPE offered a costless, portable, sensitive, stable and reproducible sensor for detection of these drugs in pharmaceutical dosage and human fluid.

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Introduction

Hypertension is a major risk factor for many serious problems such as heart attacks, strokes, disability and might leading to premature death over the world [1]. Blood pressure is recorded usually with two numbers including systolic and diastolic pressures which describe the pumping and resistance of blood flow around the body, respectively. Long-term treatment is available and several classes of antihypertensive drugs are currently available in the market such as β-blockers, calcium channel blockers, angiotensin converting inhibitor, angiotensin II receptor antagonists and diuretics [2]. While, lowering in cerebral blood flow and raises in cerebrovascular resistance was observed in cerebral hemodynamics. Therefore, the sensitive and on-site determination of the antihypertensive drugs in pharmaceutical samples and biological fluids is highly desirable for diagnostic and biomedical researches.

Propranolol hydrochloride (PRO) is chemically known as 1-(isopropylamino)− 3-(1-naphthyloxy)− 2-propanol. It is a non-selective β-blocker used in treatment of hypertension, angina pectoris and cardiac arrthmias [3]. PRO is a non-selective prototype beta-adrenergic receptor-blocking agent, it possesses other autonomic nervous system activity and specifically competes with β-adrenergic receptor-stimulating agents for available receptor in bronchi [4]. It causes severe respiratory problems such as asthma and adult respiratory distress syndrome at higher concentrations in plasma [5]. Furthermore, it has a harmful effect on phospholipid-based bilayers of cell membranes which play a fundamental role in the cell protection. Disordered bilayers (lamellar powders) and highly curved structures were found in the presence of propranolol [6]. It is also abused in sports involving little physical activity to decrease cardiac, contraction, heart rate and coronary blood flow [7]. PRO has been included in the list of forbidden drugs by the International Olympic Committee. It is rapidly metabolized after administration, thus trace concentrations of the propranolol in biological fluids is difficult to detect.

Timolol (TIM) chemically designed as (S)− 1-[(1,1-dimethyl)amino]− 3-[[4-(4-morpholinyl9-1,2,5-thiadiazol-3-yl]oxy]−2-propanol, is a nonspecific β-adrenergic blocker effective for treating hypertension, arrhythmias and angina pectoris [8]. It is the first β-blocker used to decrease ocular hypertension in glaucoma. It is highly effective compared to the modern β-blockers, thus it remains recommended up to date [9].

Amiloride hydrochloride (AMI) chemically described as 3,5-Diamino-6-chloro-N-(diaminomethylidene) pyrazine-2-carboxamide, is orally administered potassium-sparing diuretic which reduces blood pressure by inhibition of sodium ion influx through ion channels in the luminal membrane of nephron [10]. The main side effect of AMI is hyperkalaemia [11].

Triamterene (TRI) is a potassium-sparing diuretic used in the treatment of hypertension and oedema associated with congestive heart failure, cirrhosis of the liver, nephritic syndrome and idiopathic and drug-induced oedema [12]. It inhibits the reabsorption of sodium ions that exchanged by potassium and/or hydrogen ions in distal renal tubule and collecting duct [13]. In recent years, TRI has been abused in sports to enhance the performance of athletes. It decreases the body weight especially in sport activities when the competitors are classified into weight categories. Further, TRI increases the volume of urine and thus lowing the concentration of undesirable drugs in urine though dilution and prevent their analysis [14].

Amlodipine (AML) is a parent drug of calcium-channel blockers group that inhibits inward calcium channel stream in different tissues including the vascular smooth muscle and myocardium [15]. It has been used effectively as anti-hypertensive and anti-anginal agent because it has a greater selectivity for vascular smooth muscle than myocardium, thus its main effect is vasodilatation [16]. Monitoring of such antihypertensive drugs in biological fluids is important not only in clinical and pharmaceutical practices but also in the field of doping control.

Several spectrophotometric methods have been reported for determination of the antihypertensive drugs in pharmaceutical formulations [17], [18], [19], [20]. However, the poor sensitivity limits their applicability. On the other hand, different chromatographic techniques were employed including high performance liquid chromatography (HPLC) [21], [22], [23], [24], high performance thin layer chromatography (HPTLC) [19], [20], [25], and gas chromatography (GC) [26], [27], [28]. These chromatographic methods showed high sensitivity and selectivity in biological fluids but they are time consuming, require complicated extraction procedures, highly skilled technician and sophisticated instruments. Over the last decades, electrochemical methods have been widely explored for point-of-care detection because they offered accurate, sensitive and yet simple and cheap determinations in a relatively short analysis time without any tedious pre-treatment of the samples. The glassy carbon (GC) [29], [30], boron doped diamond electrode (BDD) [31], [32], [33], [34], [35], modified pyrolytic graphite (EPPG) [36], [37], silicon-based membrane [38], carbon nanotube/silicone rubber composite [39], modified glassy carbon electrode [40], [41], [42], [43], [44], [45], [46], [47], [48], [49], [50], modified carbon paste electrode [51], [52], [53], [54], [55], dropping mercury electrode (DME) [56], [57], [58], [59], [60], gold electrode [61], [62], nitrogen-containing tetrahedral amorphous carbon electrode [63], palladium nano-particles coated multi-walled carbon nanotubes/ nafion composite [64], graphite-epoxy composite electrode modified by tosyl-functionalized magnetic particles [65] and pencil graphite electrode [66], [67], and screen-printed electrode [68] were employed for electrochemical detection of several antihypertensive drugs (Table S8). Although the unmodified/bare macro-electrodes offer simplicity and cost-less methodology, continuous polishing, surface fouling, poisoning with time limit their sensitivity and reproducibility. As a result, wide range of surface modifiers such nanoparticles and carbon-based materials were used to enhance the sensitivity toward target molecule.

Recently, screen-printed graphite electrodes (SPEs) have attracted much interest because they significantly challenged the conventional three-electrode cell system due to their low cost, portability, disposability and simple and large scale production. These interesting features are leading to transfer of the electrochemical laboratory experiments to on-site field detection of various analytes [68], [69]. In order to enhance the applicability of unmodified/bare SPEs, the surfactant molecules were utilized in electroanalysis [69]. In the present manuscript we explore for the first time the individual voltammetric determination of five antihypertensive drugs (propranolol, timolol, amlodipine, amiloride and triamterene) at unmodified/bare SPEs in presence of SDS (Scheme 1). Significantly, the voltammetric signals of the antihypertensive drugs were enhanced at bare SPEs in presence of optimized concnetrations of SDS. Such simple, portable and low-cost methodology was also explored for determination of these drugs in pharmaceutical dosages and biological samples particularly to control Olympic Addict Athletes (OAA).

Section snippets

Reagents and method

All chemicals were of the analytical grade available and were used as received without further purification. Sodium dodecyl sulfate, triton X-100 and cetyltrimethylammonium bromide (CTAB) were purchased from Sigma Aldrich Co. LTD. Propranolol and amiloride were kindly supplied by Khaira Sigma Pharmaceutical Co. (Cairo, Egypt) with a purity of 98.87 ± 1.43% and 98.52 ± 1.76%, respectively. Triamterene and timolol were kindly supplied by EIPICO Pharmaceutical Co. (Cairo, Egypt) with a purity of

Results and discussion

To explore the effect of aggregated SDS molecules at the SPEs, the electrochemical oxidation of PRO was studied as an example of antihypertensive drugs by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in absence and presence of 0.04 mg/mL SDS. Fig. 1a shows the CV curves of 9.0 μM PRO using unmodified SPEs in B. R. buffer pH 7.0. The SPEs give rise to a unique and enhanced voltammetric signal of PRO in presence of SDS. Further, the Nyquist diagram of 9.0 μM PRO drug

Conclusions

A simple and costless voltammetric method for determination of PRO, TIM, AML, AMI, and TRI antihypertensive drugs were developed by utilizing the promising characteristics of unmodified SPEs in presence of SDS. The results revealed that, the SDS accumulated at the graphitic surface of SPEs which alter the electrode/solution interface characteristic and hence increase the electrochemical signals by about 10 folds in a simple manner without any needs for tedious surface modification steps.

Acknowledgements

The authors acknowledge funding from a British Council Institutional Link grant and Science and Technology Development Fund in Egypt (STDF) (No. 172726574, Project ID 18435) for the support of this research.

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