Analytica Chimica Acta 689 (2011) 5259

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Analytica Chimica Acta

journal homepage: www.elsevier.com/locate/aca

Application of an Hg2+ selective imprinted polymer as a new modifying agent for the preparation of a novel highly selective and sensitive electrochemical sensor for the determination of ultratrace mercury ions
Taher Alizadeh a, , Mohamad Reza Ganjali b , Mashaalah Zare b
a b

Department of Applied Chemistry, Faculty of Science, University of Mohaghegh Ardabili, Ardabil, Iran Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran

a r t i c l e

i n f o

a b s t r a c t
A simple and very selective electrode, based on a mercury ion imprinted polymer (IIP), and its application for the determination of Hg2+ ions in the real samples is introduced. Mercury ion selective cavities were created in the vinyl pyridine based cross-linked polymer. In order to fabricate the sensor carbon particles and polymer powder were mixed with melted n-eicosane. An explicit difference was observed between the responses of the electrodes modied with IIP and non imprinted polymer (NIP), indicating proper performance of the recognition sites of the IIP. Various factors, known to affect the response behavior of selective electrode, were investigated and optimized. The interference of different ionic species with the response of the electrode was also studied. The results revealed that, compared to previously developed mercury selective sensors, the proposed sensor was more selective, regarding the common potential interferer. This sensor showed a linear response range of 2.5 109 5.0 107 M and lower detection limit of 5.2 1010 M (S/N). The sensor was successfully applied to the determination of mercury in real samples. 2011 Published by Elsevier B.V.

Article history: Received 3 October 2010 Received in revised form 1 January 2011 Accepted 18 January 2011 Available online 25 January 2011 Keywords: Hg2+ imprinted polymer Electrochemical sensor Carbon paste electrode Ultratrace level

1. Introduction Mercury is one of the most toxic elements in the environment, because of its high reactivity, its extreme volatility and its relative solubility in water and living tissues [1]. Contamination of the environment with mercury has unfortunately remained a serious problem, despite noticeable efforts in recent years [24]. The element is also famous for the fact that ionic mercury and its derivatives tend to bioaccumulate in the human body which leads to the gathering of high concentrations of the element, which can in turn cause symptoms such as weakness, sleeplessness, paranoia, excessive salivation, skin itching and swelling, fever, memory loss, elevated blood pressure, tremors, gingivitis, excitability etc. Mercury poisoning can result from inhaling its vapor, its ingestion, injection or absorption through the skin and does most of the damage to the neurologic, gastrointestinal, and renal systems [58]. Determination of trace levels of mercury is of great urgency and hence great efforts have been made to analyze the element in trace levels by means of a wide range of spectrometric methods such as atomic uorescence spectrometry, atomic absorption spectrometry and UV spectrophotometry [912]. These techniques are cost

Corresponding author. Tel.: +98 451 5514702; fax: +98 451 5514701. E-mail address: alizadeh@uma.ac.ir (T. Alizadeh). 0003-2670/$ see front matter 2011 Published by Elsevier B.V. doi:10.1016/j.aca.2011.01.036

intensive, time consuming, hard to use and more importantly not suitable for the task of in situ testing and monitoring. On the other hand, electrochemical methods are the most favorable techniques for the determination of metal ions because of their high sensitivity in addition to low costs, ease of operation and portability. Stripping analyses of mercury have been reported by using different electrodes such as gold electrodes [13], iridium electrodes [14] and gold coated carbon electrodes [15]. In order to enhance the sensitivity and selectivity of the electrochemical determination of mercury, chemical modication of electrodes has received increasing attentions in the past decades. Numerous studies have been directed to the determination of mercury(II) ion by modied electrodes. The modiers used have included organic chelating groups [1623], polymers [2429], silica and solgel [3034], clays [3540] and clays grafted with organic chelating groups [41]. Most of the procedures, however, have faced difculties achieving the sensitivity required for the determination of low levels of mercury(II) ion in some real samples. Moreover, these materials do not provide a proper selectivity towards Hg2+ in the presence of some potential interferers like Cd2+ , Pb2+ , and Cu2+ . Therefore, there is still an urgent demand for a highly selective modier in this eld. Molecular imprinted polymers (MIP) are new high selective synthetic receptors with molecular recognition sites designed for a particular analyte. MIP technology has been developed as a method

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for the preparation of synthetic receptors by polymerization of self assembled complexes, formed by functional monomers and a template in the pre-polymerization mixture [4248]. This technology can also be used for the preparation of polymers containing inorganic cation selective sites as the so-called ion imprinted polymers (IIP) [4952]. Different kinds of imprinted polymers have so far been reported for the recognition of mercury ions [5356]. Recently, we have reported several papers describing the application of MIP particles as a recognition element of the electrochemical sensors such as voltammetric and potentiometric sensors for different kinds of molecular analytes [5760]. Due to the high selectivity of these materials, the electrode containing imprinted materials tends to show selective behaviors. Besides, this modifying agent can pre-concentrate the analyte in the electrode due to the high adsorption capacity of these materials. The obtained interesting results from the previous works provoked us to design a novel Hg2+ electrochemical sensor, using ion imprinted polymers. As mentioned before, each of the described modifying agents, previously used in Hg2+ electrodes, possessed some advantages and suffered from some shortcommings. For example, organic chelating agents provide a moderate selectivity, but suffer from instability in the response. Zeolite and solgels provide high stability and adsorption capacity, while suffering from an inherently low selectivity. Although, polymeric materials like peruorinated polymers provide considerably lower detection limit [28], they function based on the ion exchanging mechanism and their selectivity is thus not considerable. On the other hand, it seems that the electrodes modied with Hg2+ IIP possesses approximately the advantages of most of the previously stated modifying agents. IIP has a high selectivity even more than organic chelating agents. It provides high adsorption capacities comparable with that of clays and zeolite, providing high sensitivity and lower detection limit. Also, IIP materials usually show a high stability and durability against harsh chemical environments. In other words, electrodes modied with ion imprinted polymers bring together the advantages of different kinds of modifying agents in a single modied electrode. Moreover, both IIP and carbon paste are cheap materials and thus a carbon paste electrode modied with IIP can provide an efcient and cheap sensor for Hg2+ determination. In this work, the Hg2+ selective imprinted polymer was synthesized based on a new formulation. The obtained Hg2+ imprinted polymer was used as a modifying agent and mixed with carbon powder in the presence of melted n-eicosane in order to prepare a Hg2+ selective voltammetric sensor. The prepared electrode showed very interesting analytical characteristics.

2.2. Preparation of Hg(II) imprinted polymer and modied electrode In order to prepare IIP, 1 mmol Hg(NO3 )2 and 4 mmol 4-vinyl pyridine were dissolved in 20 mL of DMSO. Then, 0.15 g of the initiator (2,2 -azobisisobutyronitrile) and cross-linker (EDMA), dissolved in 3 mL DMSO, was mixed with the previous solution and purged with N2 gas for 10 min. The polymerization was carried out in a water bath at 70 C for 24 h. The obtained polymer particles were rstly washed with ethanol and then washed with a 0.1 M HCl solution. Finally, the particles were washed with distilled water and dried at 60 C. The NIP was prepared, using the same protocol in the absence of Hg(II). The prepared IIP and NIP were used for carbon paste electrode fabrication. 2.3. Preparation of the sensors For construction of the sensor (IIP-CP), 0.02 g graphite was homogenized in a mortar with 0.005 g of powdered IIP for 10 min. Subsequently, n-eicosane, 0.007 g was melted in a dish in a water bath, and heated at 4550 C. The graphite/IIP blend was then added to the melted n-eicosane and mixed with a stainless steel spatula. The nal paste was used to ll a hole (2.00 mm in diameter and 3 mm in depth) at the end of an electrode body, previously heated at 45 C. After cooling at room temperature, the excess of solidied material was removed with the aid of a sheet of paper sheet. The electrode can be reused after each experiment by moving the electrode surface on a paper sheet in order to rub out a thin layer of the electrode surface. 2.4. Determination procedure The prepared electrode was inserted into the solutions containing the Hg2+ (pH = 2.5) while being stirred. Then, the electrode was inserted into the washing solution (water-neutral pH), remaining in this solution for 15 s. The electrode was nally placed in the electrochemical cell containing 10 mL of HCl (0.12 M). At rst, a negative pre-potential of 1.2 V was applied to the electrode for 30 s and then a differential pulse voltammetry was performed from 0.10 to 0.3 V. 3. Results and discussion 3.1. Mercury ion imprinted polymer Several formulations have already been reported for preparation of mercury ion imprinted polymers. Liu et al. [56] have prepared IIP for mercury by copolymerizing mercury chloride, diazoaminobenzene (DAAB) and vinylpyridine (VP) using ethyleneglycoldimethacrylate (EGDMA) as a cross-linker. Another work in this eld is from Denizli and his coworkers [53] who applied N-Methacryloyl-(l)-cysteine as both a functional monomer and complexing agent. Copolymerization of the methacrylic acid as the monomer, and trimethylolpropane trimethacrylate as the cross-linking agent, in the presence of Hg(II)-1-(2-thiazolylazo)2-naphtholcomplex is another method reported by Dakova et al. [55]. Recently, Singh and Mishra [54] have described a new formulation for Hg(II)-ion-imprinted polymer (IIP) by the formation of a binary complex of mercury with 4-(2-thiazolylazo) resorcinol and its thermal copolymerization with methacrylic acid (monomer) and ethylene glycol dimethadrylate (crosslinker), and in cyclohexanol as a porogen. In all of the described procedures an additional ligand has been applied for preparing IIPs, which increases the complexity of the preparation method. In the present work, however, we applied a

2. Experimental 2.1. Instrument and reagents Electrochemical data were obtained with a three-electrode system using a PGSTAT302 Metrohm potentioastat/galvanostat. The carbon paste electrodes modied with IIP or non imprinted polymer (NIP) were used as a working electrode. A platinum wire and an Ag/AgCl electrode were used as the counter and reference electrodes, respectively. Vinyl pyridine (Merck, Germany) was puried by distillation under reduced pressure. Ethylene glycol dimethacrylate (EDMA) (SigmaAldrich, USA), was distilled under reduced pressure in the presence of hydroquinone inhibitor and stored at 4 C until use. 2,2 -(2-Methyl propionitrile) was obtained from Acros Organic, Geel, Belgium. Dimethyl sulfoxide (DMSO) and Hg(NO3 )2 4H2 O were from Merck, Germany. Other chemicals were of analytical grade and were purchased from Merck, Germany.

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Fig. 1. Schematic representation of the method applied for mercury ion imprinted polymer synthesis.

new and simple method for preparing mercury imprinted polymer. According to the method of current work, vinyl pyridine acted as both the functional monomer and complexing agent. This way, mercury ions simply interacted with vinyl pyridine in a mole ratio of 4:1 (monomer/cation) in dimethyl sulfoxide. Then, the polymerization started in the presence of the initiator. Fig. 1 schematically shows the route for preparing IIP according to the current work. Primary evaluation of the obtained IIP showed a high capability of the polymer for adsorption of Hg2+ in comparison to NIP. 3.2. Comparison of the IIP-CP electrode with NIP-CP electrode The carbon paste electrode modied with IIP was incubated in an Hg2+ solution, and meanwhile the solution was continuously stirred. Then, the electrode was inserted in the electrochemical cell and a negative potential was applied to the electrode. Subsequently, the differential pulse voltammetry technique was applied for the determination of mercury. The same experiment was carried out in the case of the electrode modied with NIP. In another experiment, the IIP-CP and NIP-CP electrodes were inserted in a washing solution for 10 s, after being removed from the Hg2+ solution. The obtained voltammetric signals of the two mentioned electrodes are shown in Fig. 2. It can be seen that the signal obtained for the IIPCP electrode is noticeably higher than that of the NIP-CP electrode, indicating the existence and proper functioning of the selective cavities in the IIP, created in the polymerization step. Washing of the electrodes, after removing them from the analyte solution, decreased both electrode signals indicating removing of weakly adsorbed ions on the IIP or NIP surface sites. However, the decrease rate in the NIP signal is higher than that in the IIP-CP electrode. This can be related to the fact that most of the adsorbed mercury ions are located in the selective sites of the IIP that are attracted strongly and specically to the IIP, while the sites responsible for Hg2+ adsorption in the NIP are surface adsorption sites of weak and

nonselective nature. The initial response of CP electrode as well as its response after washing is also represented in Fig. 2. It is clear that the response of CP electrode for Hg2+ is small and it is considerably decreased by applying washing step, indicating lower afnity of the graphite and binder for Hg2+ , compared to NIP and especially IIP.

Fig. 2. Comparison of differential pulse voltammetry responses of IIP-CP electrode and NIP-CP electrodes with and without washing step; anodic stripping voltammetry conditions: E-conditioning = 1.2 V, conditioning time = 30 s, E-step = 0.01 V, E-pulse = 0.1 V, pulse time = 0.01 s, and scan rate = 0.1 V s1 .

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Fig. 3. Evaluation of selectivity of developed sensor; responses of the electrode for Hg2+ (1 107 ) (I), Cu2+ (II) and Cd2+ (III); (a) 1 104 , (b) 5 105 , (c) 1 105 ; extraction time = 20 min, stirring rate = 700 rpm; anodic stripping voltammetry conditions: E-conditioning = 1.2 V, conditioning time = 30 s, E-step = 0.01 V, E-pulse = 0.1 V, pulse time = 0.01 s, and scan rate = 0.1 V s .

3.3. Evaluation the selectivity of the sensor As described in Section 1, numerous kinds of modifying agents have been introduced for the selective pre-concentration of mercury ions, but the interference effect of some cations such as Cu2+ , Bi3+ , Pb2+ , Fe3+ , Ag+ , Au3+ and Cd2+ is still the main problem in the eld. The interference effect can be categorized into two sections: (a) the interference effects caused by the metal ions which are easily reduced to the metallic state such as: Au3+ , Ag+ , Pt4+ , pd2+ , Cu2+ and Pb2+ . These ions show their interference effect in the methods comprising the pre-concentration step, performed through the application of reduction potentials. These ions are yet known as the main interfering ions in the voltammetric determination of mercury due to the possible co-deposition [37,61]. (b) The interference effects caused by the metal ions such as Cd2+ , Bi3+ , Ag+ which can interact with thiol groups, included mainly in the chelating agent used for modifying the mercury selective electrodes. These interferes inuence the determination of mercury even in open circuit deposition of mercury on the electrode [23,41]. The selectivity of the method against two representatives of the described potential interfering groups including Cu2+ (group 1 and 2) and Cd2+ (group 1) were investigated. Fig. 3 shows the obtained voltammetric signals of the target ion in the concentration of 1 107 M and Cu2+ and Cd2+ at different concentrations. As it is clear, when the concentrations of both Cd and Cu are 100 times as much as that of Hg2+ no signal is shown by the IIP modied electrode. At Cd2+ concentration 500 times as much as that of Hg2+ a clear signal appears for Cd2+ . These results are very interesting in comparison to the selectivity results of previously reported works in the case of these cations. It must be noticed that the signals observed for these cations in the electrode are in the potential ranges that are far enough from the Hg potential, approximately meaning that these ions have no interference in the determination of Hg even at higher concentrations of the described interferer ions.

were changed in the xed conditions of extraction and voltammetric determination and the obtained responses were used for conclusion. The IIP-CP electrode was prepared with a xed amount of carbon and n-eicosane and different amounts of IIP. The fabricated electrode, in each case, was used for the extraction and determination of Hg2+ . The obtained results are presented in Fig. 4(I). It is clear that the maximum response for the prepared sensor appears in the IIP amount of 0.005 g. The higher the amounts of IIP are the sensor response increases due to providing more recognition sites on the electrode surface. However, increasing the IIP above a threshold amount, leads to a decrease in the response of the prepared sensor, most probably due to decrease in the conductivity of the electrode surface. The effect of amounts of carbon and n-eicosane on the response of the prepared electrode was investigated by varying the amounts of these parameters in the IIP-CP electrode, followed by recording the obtained signal. The results are shown in Fig. 4(II) and (III). From the corresponding curves, the optimum amount of carbon and n-eicosane were found to be, 0.02 and 0.007 g for carbon and n-eicosane amounts, respectively. Initially, increasing the carbon content of the IIP-CP electrode was found to lead to an increase in the electrode response, but, after a denite point, further carbon content increasing resulted in lowering the corresponding signal. The rst increase in the response can be related to the enhancement of electron transferring capability of the electrode in the presence of higher carbon content. Furthermore, the electrode response decreased with increasing the carbon content, can be attributed to the fact that the more carbon leads to a decrease in the content of the IIP on the electrode surface. It is also clear that an optimum amount of n-eicosane is required for IIP-CP electrode preparation. Presence of higher amounts of the binder (n-eicosane) in the IIP-CP electrode leads to a decrease in electrode response, because of decreasing the electrode surface conductivity.

3.4. The effect of the electrode composition on the MIP-CP response for Hg2+ In order to nd the best composition for the IIP-CP electrode, different amounts of ingredients including IIP, carbon and n-eicosane

3.5. Washing effect As described previously, washing of the electrode results in the removal of weakly adsorbed species from the electrode surface. This can be used for improving the sensor selectivity and

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Fig. 4. Evaluation of the effect of electrode composition on its response.

omitting the interference effects, if proper washing conditions are applied. It was found that pure water is a proper washing solvent for this aim. In this washing media the NIP-CP signal was considerably decreased, while the IIP-CP signal decrease as a result of washing was not considerable. Different organic solvents such as ethanol, methanol, acetone and acetonitrile were added to the water (2% in water) and tested as the washing solution. No improvement for aimed signal from the mentioned mixtures was observed. The optimum time of immersing the electrode in the washing solution was also investigated. It was found that the difference between the response of IIP-CP and NIP-CP increased till 15 s and afterwards the signal reached to partly steady state. Thus, 15 s was chosen as optimal washing time. 3.6. The effect of Hg2+ extraction conditions on the electrode response In order to nd the optimum electrode incubation time, the prepared electrodes were inserted into the Hg2+ solutions for various times. Next, the electrode was removed from the solutions, followed by differential pulse voltammetry. The obtained results are shown in Fig. 5(I). According to this gure, increasing the extraction time leads to an intensive increase in the extraction of mercury ion in the electrode till about 15 min. After this period, the increase in the response is not considerable. In order to decrease the analysis time, the 15 min was selected for the extraction time. The pH of the extraction solution was also checked and its effect on the Hg2+ extraction in the electrode was studied. For this

purpose, the prepared electrode was inserted into solutions with various pH values where they were incubated for 10 min at a constant stirring rate. After the mentioned time, the electrode was removed from the solution and immersed into the solution of the electrochemical cell. The results of this experiment are shown in Fig. 5(II). As can be seen, stabilizing the pH is crucial task in this work. The optimum pH for the proposed method was found to be 2.5. Decreasing of the pH, lower than 2.5, decreases the electrode signal due to the decrease in the amount of the target ion extracted into the electrode. This is probably because of the protonation of nitrogen moieties of the selective sites of the IIP, that weaken the interaction of Hg2+ with the vinyl pyridine groups, existing in the selective sites of the IIP. At higher pH values (above 2.5) a considerable decrease in the electrode signal can be distinguished probably because of tendency of Hg2+ ions to precipitate as hydroxide sediments at higher pH values. In order to optimize the stirring rate and extraction period, Hg2+ was extracted in the prepared IIP-CP electrodes at various stirring rates, whereas the other extraction parameters were the same and constant. The obtained results, showing the variation of the voltammetric electrode signal to mercury against the stirring rates, are presented in Fig. 5(III). As can be seen, the greater the stirring rate, the higher the electrode response for Hg2+ , indicating the considerable effect of the stirring rate on the Hg2+ extraction into the IIP-CP electrode. The growth in the voltammetric response with increasing the stirring ratecontinues up to 500 rpm. However, further increasing of the stirring rate does not considerably inuence the amount extracted. Therefore, a stirring rate of 500 rpm was chosen as optima for this variation.

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Fig. 5. Evaluation of the extraction conditions effects on the electrode response.

3.7. The effect of pH and electrolyte type of electrochemical determination After accumulation of mercury ions on the electrode surface at open circuit condition and its washing with the washing solution, the electrode was inserted into an electrochemical cell, containing the electrolyte solution with various pH values. This was carried out in order to investigate the effect of the electrolyte pH on the electrode response. It was found that the acidity of pH is crucial task for obtaining strong and stable signals. Next, the effects of different electrolytes, providing acidic media for the voltammetric analysis, were tested. The obtained results are illustrated in Fig. 6. It is clear that the type of the electrolyte considerably inuences the response behavior of the electrode, with respect to the signal amplitude, background current and potential shift. It can be seen that HCl (0.12 M) leads to better results, in terms of higher signal amplitude and lower background current.

3.8. Analytical characterization After the optimization and establishment of the determination method for the prepared IIP-CP sensor, interference of various species was examined. The tolerance limit was established as the maximum concentration of foreign species that caused a relative error of 5% in the analytical signal. For 50 nM of mercury(II), the developed sensor was not affected by the presence of different alkaline and earth alkaline cations even in concentrations having 1000-fold excess to the Hg2+.

Fig. 6. Effect of different electrolyte on the sensor response to Hg2+ .

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Table 1 Determination of Hg(II) in water samples containing 0.025 M Hg2+ (adjusted by spiking). Sample IIP-CP Hg Tap water River water (garasou, ardabil) Lake water (shoorabil, ardabil)
2+

Reference method Recovery (%) 96.0 104.0 108.0 RSD% (n = 5) 2.31 3.70 3.9 Hg2+ found (M) 0.022 0.027 0.029 RSD% (n = 3) 6.6 5.9 6.9

found (M)

0.024 0.026 0.027

95%, indicating the signicance and applicability of the developed technique for reliable determination of trace amount Hg2+ in real samples. 4. Conclusion The new electrochemical sensor for determination of mercury ions at trace levels based on the application of IIP as a novel modifying agent in the carbon paste electrode showed high selectivity for mercury in the presence of common potential interferers was found to show satisfactory results. The IIP in the carbon paste electrode acted as the selectivity inducing agent and also played the role of a pre-concentrator to exhibit high selectivity as well as low detection limit. References
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Fig. 7. Calibration curve of the developed mercury ion sensor in the optimized conditions; inset in the linear range of the calibration curve.

A vast majority of metal ions were found not to signicantly interfere in the detection of Hg(II) including Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II) or Pb(II), at a concentration 400 times as much as that of the target analyte, giving rise to no signicant variations (within the standard deviation of the method) in the Hg(II) signal. Only Cd2+ was found to show some degree of interference at concentration 200-fold excess to that of Hg(II). The response of the prepared and optimized IIP-CP sensor towards Hg2+ concentration variations was checked. The calibration graph (shown in Fig. 7) of the prepared sensor showed a linear relationship in Hg concentration in the range of 2.5 109 5.0 106 M with a detection limit of 5.2 1010 M (S/N = 3). Each point of the calibration graph is the average of three replications. 3.9. Determination of Hg2+ in real samples Determination of mercury(II) was carried out in real water samples. The samples were tested before addition of mercury(II) with optimized sensor and it was found that all of them were mercury(II) free. 50 mL of samples were then spiked with mercury(II) till the nal concentration reached 0.025 M. the pH of solutions was adjusted to 2.5. The determination method was then performed step by step, according to the proposed procedure, using the developed sensor. The results can be seen in Table 1. The obtained percent recoveries and corresponding standard errors indicate that the sensor has a proper capability for accurate and precise determination of mercury in real samples. The signicance of the developed method was also tested. For this aim the previous samples were again analyzed by differential pulse stripping voltammetry after sorption of mercury vapor on gold-plated electrode as the selected reference method [62]. The results (shown in Table 1) were compared statistically with those of the newly developed sensor. There was no signicant difference between these results at condence level of

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