Sensors and Actuators B 245 (2017) 605–614 Contents lists available at ScienceDirect Sensors and Actuators B: Chemical jo ur nal home page: www.elsevier.com/locate/snb Development of a highly selective and sensitive electrochemical sensor for Bi 3+ determination based on nano-structured bismuth-imprinted polymer modified carbon/carbon nanotube paste electrode Taher Alizadeh a, , Negin Hamidi a , Mohamad Reza Ganjali a,b , Parviz Nourozi a a Department of Analytical Chemistry, Faculty of Chemistry, University College of Science, University of Tehran, P.O. Box 14155-6455, Tehran, Iran b Biosensor Research Center, Endocrinology & Metabolism Molecular-Cellular Sciences Institute, Tehran University of Medical Sciences, Tehran, Iran a r t i c l e i n f o Article history: Received 13 October 2016 Received in revised form 20 January 2017 Accepted 2 February 2017 Available online 3 February 2017 Keywords: Bismuth Ion-imprinted polymer Carbon nanotube Carbon paste Voltammetric sensor a b s t r a c t A new nano-structured bismuth(III)-imprinted polymer was prepared by copolymerization of Bi(III)- methylene succinate complex and ethylene glycol dimethacrylate in acetonitrile via precipitation polymerization technique. The polymeric nanoparticles were then used as the Bi 3+ selective modifier of a carbon/carbon nanotube paste electrode. Bismuth ions were accumulated on the surface of the electrode, immersed in the Bi 3+ solution for a definite time. Then, the anodic striping differential pulse voltammetric signal of the modified electrode was recorded as analytical signal which was significantly higher than that recorded by the non-imprinted polymer based electrode, at the same experimental con- ditions. Compared to the previously reported carbon paste electrodes, this sensor was more selective, regarding potential interfering species of Cu 2+ and Ag + . The electrode exhibited a dynamic linear response range of 0.2–2 mol L -1 and detection limit of 8.9 nmol L -1 for Bi 3+ measurement. The sensitivity of the sensor was 112.25 A M -1 , indicating an excellent sensitivity of the developed sensor. The sensor was successfully applied for the electrochemical determination of Bi 3+ ions in environmental, pharmaceutical and biological samples. © 2017 Elsevier B.V. All rights reserved. 1. Introduction Bismuth and its compounds are presently employed in the fab- rication of semiconductors and alloys. Bismuth compounds have important applications in pharmaceutical preparations. They are employed as antibacterial, anti-HIV and radiotherapeutic agents. Furthermore, bismuth compounds are widely used in the treatment of syphilis, helicobacter pylori induced gastritis and dermatologi- cal disorders. Bismuth is also utilized for the preparation of creams and hair dyes [1–3]. However, some toxic effects in humans such as nephropathy, osteoarthropathy, hepatitis and neuropathology have been assigned to bismuth compounds [2]. The development of selective separation or determination methods for bismuth is a challenge because of low level concentra- tions of bismuth in natural samples and strong interference effect of sample matrix on its determination [1]. Corresponding author. E-mail addresses: talizadeh@ut.ac.ir, taa 55@yahoo.com (T. Alizadeh). Several instrumental methods including coupled plasma atomic emission spectrometry (ICP-AES [4], ICP mass spectrometry (ICP- MS) [5], atomic absorption spectrometry (AAS) [6] and atomic fluorescence spectrometry (AFS) [7] have already been introduced for the measurement of bismuth. These techniques are sensitive and selective; but, they require expensive instruments and time consuming sample pretreatment [2]. Generally, electrochemical determination of Bi 3+ is complex due to the strong tendency of bismuth salts to hydrolysis even at acidic pH conditions. Consequently, very acidic medium must be used to avoid hydrolysis of Bi(III) [8]. In spite of this, electrochemi- cal methods such as potentiometric stripping analysis (PSA) [9], anodic stripping voltammetry (ASV) [10–13] and cathodic stripping voltammetry (CSV) [14,15] have been proposed for the determina- tion of bismuth. Such described methods are comparatively simple and provide rapid response and high sensitivity; but, they all utilize toxic mercury, as working electrode [2]. Carbon paste electrodes (CPEs) have been extensively used for the electrochemical monitoring of metal ions, because of http://dx.doi.org/10.1016/j.snb.2017.02.024 0925-4005/© 2017 Elsevier B.V. All rights reserved.