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Voltammetric Sensing of Mercury and Copper Cations at Poly(EDTA-like) Film Modified Electrode
George O. Buica,a Christophe Bucher,b Jean-Claude Moutet,b* Guy Royal,b Eric Saint-Aman,b Eleonora M. Ungureanua
Faculty of Applied Chemistry and Material Sciences, University Politehnica of Bucharest, Splaiul Independentei 313, 060042, Bucarest, Romania b Universite Joseph Fourier Grenoble 1, Departement de Chimie Moleculaire, UMR CNRS-5250, Institut de Chimie Moleculaire de Grenoble, FR CNRS-2607, BP 53, 38041, Grenoble Cedex 9, France *e-mail: jean-claude.moutet@ujf-grenoble.fr Received: August 18, 2008 Accepted: October 7, 2008 Abstract Complexing polymer-coated electrodes have been synthesized by oxidative electropolymerization of ethylenediamine tetra-N-(3-pyrrole-1-yl)propylacetamide (monomer L). The presence of four polymerizable pyrrole fragments on the same EDTA skeleton was thought to confer enhanced rigidity and controlled dimensionality to the resulting complexing materials, which were used for the electrochemical detection of Hg(II), Cu(II), Pb(II) and Cd(II) ions by means of the chemical preconcentration-anodic stripping technique. The polyamide electrode material showed particularly a significant selectivity towards mercury ions, even in the presence of a large excess of other metal cations. Moreover, the use of imprinted polymer-coated electrodes prepared by electropolymerization of L in the presence of metal cations turned out to significantly improve the detection limits, down to 5 1010 mol L1 for Hg(II) and Cu(II) species. Keywords: Functionalized polypyrrole, Modified electrodes, Imprinted polymer, Voltammetric sensing, Metal ions analysis DOI: 10.1002/elan.200804386
a

1. Introduction
A significant increase in the level of toxic species in natural environments due to human activities has been recorded in the last few decades. Metals such as copper, cadmium, lead and mercury, continuously accumulating into ecosystems through industrial processes, are non bio-degradable species whose life-threatening hazards mostly depend on their chemical forms and exposure levels [1]. Among those bioaccumulating metals, mercury is one of the most poisoning substance to humans and animals [2]. Determination of trace levels of this element in the environment is thus a highly important, yet challenging analytical problem. To accurately determine environmentally toxic trace levels of mercury, highly sensitive and selective methods still need to be developed. Spectroscopic techniques such as cold vapor generation followed by atomic absorption spectrometry [3], cold vapor atomic fluorescence spectrometry [4, 5], inductively coupled plasma mass spectrometry [6, 7], capillary zone electrophoresis-inductively coupled plasma mass spectrometry [8] and plasma atomic emission spectroscopy [9] have been successfully used for mercury detection. These methods generally have good sensitivity, reproducibility and can meet practical needs. However, their use requires expensive instruments, well-controlled experimental conditions, sample making and relatively large samples volumes. There are thus currently great demands for simple
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methods allowing rapid measurements of trace mercury in contaminated samples. Electrochemical detection of trace metals offers several advantages, including remarkable sensitivity, inherent miniaturization and portability, remote monitoring and decentralized measurements, low cost and compatibility with turbid samples and with advanced micromachining technologies [10 12]. Stripping voltammetry using mercury working electrodes, based on amalgams formations and stripping of electroprecipitated metals [13], has proved to be one of the most sensitive electrochemical method to analyze trace metals. Because of the toxicity of mercury, alternative solid electrode materials such as bare gold [14], iridium [15], carbon disk [16], bismuth-film coated [17], or boron-doped diamond [18] electrodes, as well as gold plated graphite electrodes [19 21] or screen printed carbon electrodes [22, 23], have been used as possible alternative to mercury. Moreover, stripping analysis using chemically modified electrodes (CME) exhibit however higher selectivity due to specific interactions between metal ions and complexing matrix [24 27]. Use of CMEs furthermore greatly limits chemical interferences and allow sensing of metals as mercury or silver, which can not be analyzed with conventional mercury based anodic stripping voltammetry [28 32]. Stripping voltammetric analyses of mercury have yet been reported at solid working electrodes using carbon paste incorporating various organic [33 40] or inorganic
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Scheme 1. Synthesis of L.

compounds [41], sonogel carbon electrodes [42, 43], glassy carbon electrodes in association with ion exchange resins [44, 45], or with various electrolytes and additives [46 48]. Functionalized conducting polymer films have also received considerable attention due to their great potential as analytical electrode materials [49, 50]. Stable polymer film modified electrodes containing covalently attached dithiocarbamate [51] or EDTA [52, 53] moieties, able to sense copper, cadmium or lead, have been produced by chemical derivatization of films previously coated by electropolymerization onto electrodes. Incorporation of complexing fragments into polymeric materials can alternatively be prepared by doping or ion exchange procedures [54 56]. However the most efficient approach towards chelatingmodified electrodes lies in the direct electropolymerization of complexing monomers, producing in one step stable functionalized polymers films with controlled sizes and sites concentrations. This straightforward approach has however seldom been applied to the determination of trace metals and only few examples can be found in literature [57 60]. We have however recently reported that carbon electrodes modified by electropolymerization of pyrrole-containing monomers substituted with specific complexing groups are fully suited for the determination of trace metals [61 63]. In the present article, we report the synthesis of an original EDTA-like pyrrole-containing dendronic ligand L, and the sensing properties of polyL coated carbon electrodes (C j polyL, Scheme 1) towards Hg(II) and Cu(II) cations, using the open circuit preconcentration-anodic stripping technique. We demonstrate that the selectivity of these grafted molecular materials can be subtly tuned upon playing on complexation parameters such as pH, reduction potential, concentration, and accumulation time. The response of the chemically modified electrodes was evaluated for the analysis of mercury in the presence of Cu(II), Pb(II) and Cd(II). In contrast to the vast majority of 1D-polymers grown for monomers containing only one appended pyrrole group, the
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introduction of four polymerizable pyrrole fragments on the same EDTA skeleton was furthermore thought to confer enhanced rigidity and controlled dimensionality to the complexing materials. We especially investigated the imprinting properties of these 3D-molecular architectures engineered upon polymerizing monomers in presence of metal ions, and analyzing the effects of the imprinting approach on the analytical responses of C j polyL towards the targeted metal cations.

2. Experimental
2.1. Reagents and Materials Acetonitrile (Rathburn, HPLC grade S) and tetra-n-butylammonium perchlorate (TBAP, Fluka puriss) were used as received. Suprapur grade sodium acetate and acetic acid (Merck) were used to prepare acetate buffers. Acetate buffers were prepared by adjusting the pH of a 0.2 M sodium acetate solution to 5.5 or 4.5 through the addition of acetic acid at 0.2 mol L1, followed by dilution with distilled water to give final buffer strengths of 0.1 mol L1. The disodium salt of ethylenediamine tetraacetic acid was purchased from Roth chemicals. Copper(II) acetate (VWR, p.a, ! 98%), lead(II) nitrate (VWR, p.a, ! 9.5%), cadmium(II) nitrate (Merck, ! 99%), mercury(II) acetate (Strem Chemicals, 99%) and zinc(II) trifluoromethanesulfonate (Aldrich, 98%) were used as received. Distilled water was obtained from an Elgastat water purification system (5 MW cm). Glassware bottles were soaked in KMnO4-H2SO4, rinsed with a H2SO4-H2O2 solution, and then carefully cleaned with distilled water before use to avoid contamination. 1H-pyrrole-1-propanamine [64] and tetraethyl ethylenediaminetetraacetate [65] were prepared according to previously reported procedures. Synthesis of ethylenediamine tetra-N-(3-pyrrole-1-yl)propylacetamide (L): tetraethyl-ethylenediaminetetraace 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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Voltammetric Sensing of Mercury and Copper Cations

79 electroactivity upon transfer into pure CH3CN 0.1 mol L1 TBAP electrolyte. Apparent surface concentrations in complexing sites GL (mol cm2) were determined from the charge recorded under the polypyrrole oxidation wave by cyclic voltammetry at low scan rate (2 mV cm1), taking into account that one monomer L is linked to 4 pyrrole rings and assuming that one in three pyrrole units is oxidized [50]. Typically, films with GL between 7 109 and 108 mol cm2 were obtained using polymerization charges of 0.5 and 1 mC, respectively.

tate (500 mg, 1.23 mmol) and 1H-pyrrole-1-propanamine (750 mg, 6 mmol) were introduced in a 5 mL round bottom flask and the mixture was heated at 80 8C under argon for 15 hours. The excess of 1H-pyrrole-1-propanamine was then removed by distillation of the crude mixture under vacuum (0.1 Torr, 60 8C). The oily residue was then dissolved in a minimum of dichloromethane and a white solid product was precipitated upon adding an excess of hexanes. The latter was filtrated and well washed with hexane and diethyl ether. The resulting hygroscopic solid material was then dissolved in dichloromethane and the solution was washed with an aqueous HClO4 solution at pH 5. The organic phase was finally dried over anhydrous sodium sulfate, filtrated and evaporated under reduced pressure to afford L as a white solid (yield 65%). 1H NMR (250 MHz, CDCl3): 1.85 2.00 (m, 8H, CH2CH2CH2); 2.63 (s, 4H, NCH2CH2N), 3.13 (s, 8H, NCH2CO), 3.15 3.25 (m, 8H, NHCH2), 3.90 (t, 8H, CH2-Pyr)), 6.13 (m, 4H, -pyr), 6.65 (m, 4H, -pyr), 7.05 (bs, 4H CONH). 13C NMR (250 MHz, CDCl3): 31.2, 37.0, 47.5, 53.4, 58.7, 108.5, 120.5, 170.6. MS (positive DCI_NH3/ isobutane): 717.34 [M 1].

2.4. Accumulation of Metal Ions at Open Circuit and Voltammetric Sensing Procedures Pb(NO3)2 2H2O, Cd(NO3)2 4H2O, Cu(OAc)2 H2O, Hg(OAc)2 and Zn(CF3SO3)2 were used as metal ions sources. Before cation sensing analytical experiments the electroactivity of the polypyrrole matrix was systematically destroyed by cycling several times the modified electrode between 0.2 V and 1.2 V in a acetate buffer (pH 5.5), in order to obtain clean voltammogram in the positive potential region. Accumulation of metal ions into the polyL films was carried out at open circuit by dipping the C j polyL modified electrodes for a given time (see discussion section) into 5 mL of a stirred acetate buffer solution containing metal cations, at a given pH (4.5 for mercury ions and 5.5 for copper ions). The electrodes were then removed from the accumulation cell and washed thoroughly with purified water to remove unbounded ions from the modified electrode surface. They were subsequently transferred into an electrochemical cell containing a 0.1 mol L1 acetate buffer solution and characterized under quiescent conditions by differential pulse voltammetry (DPV). Before recording DPV curves, the accumulated metal ions were reduced for 10 min at 0.9 V for Cu(II) and for 3 min at 1.8 V for Hg(II) to ensure full reduction of the entrapped metal ions. Unless otherwise noted, each metal determination was conducted with a freshly prepared modified electrode.

2.2. Electrochemical Equipment and Procedures Electropolymerization of L in acetonitrile was carried out using an EGG PAR model 173 potentiostat equipped with a model 179 digital coulometer and a model 175 programmer. Metal cation sensing experiments were conducted in aqueous buffer (0.1 mol L1) with a CHI 660B electrochemical analyzer (CH Instruments), using a conventional three electrodes system. The working electrode was a C j polyL modified carbon disk, the counter electrode was a platinum wire and the reference electrode was Ag j AgCl in saturated NaCl. Differential pulse voltammetry (DPV) experiments were conducted at 10 mV s1 with an amplitude of 50 mV and 0.2 s pulse periods. Solutions were degassed with a stream of N2 for 20 min before each measurement and kept under a N2 atmosphere during the entire experiments, conducted at 25 8C. Radiometer Analytical PHM210 Meter Lab pH-meter was used for pH measurements.

3. Results and Discussion

2.3. Preparation of the Modified Electrodes C j polyL modified electrodes were prepared in a classical three compartments cell using conventional three-electrode system. The working electrode was a glassy carbon disk working electrode (3 mm diameter, from CH Instruments, polished with a 0.2 mm diamond paste), the counter electrodes was a platinum wire and the reference electrode was Ag j 102 mol L1 Ag in CH3CN 0.1 mol L1 TBAP. PolyL films were grown from CH3CN solutions containing L (103 mol L1) and 0.1 mol L1 TBAP, by controlled potential oxidative electropolymerization carried out at 0.85 V up to the desired charge (see the discussion section). The modified electrodes showed the regular polypyrrole based
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3.1. Preparation and Characterization of the C j polyL Modified Electrodes The targeted polyamide L was synthesized in good yield upon heating a solvent free mixture of tetraethyl-ethylenediaminetetraacetate and 1H-pyrrole-1-propanamine. The electropolymerization of L was readily achieved in acetonitrile electrolyte. The monomer displays the regular irreversible pyrrole-based oxidation peak around 0.9 V. PolyL films could be grown onto carbon disk electrode surfaces from 103 mol L1 L in CH3CN 0.1 mol L1 TBAP, upon repeated scans in the 0.2 V to 0.85 V potential range. Formation of a conducting polypyrrole film was evidenced by the growth of a quasi-reversible redox peak
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80 system centered around 0.25 V. Upon transfer into clean acetonitrile 0.1 mol L1 TBAP electrolyte, the resulting C j polyL modified electrode retains this electroactivity. PolyL films could also be grown by controlled potential oxidation at 0.85 V, i.e., at the threshold of the pyrrole oxidation wave. Modified electrodes used for cation sensing experiments have been prepared in these experimental conditions. Apparent surface concentration of complexing sites GL (mol cm2) was assessed from the charge under the polypyrrole oxidation wave, recorded by CVat low scan rate (2 mV cm1), assuming that one in three pyrrole units is oxidized [50]. Typically, dark-blue films with GL ranging from 2.5 109 to 108 mol cm2 were obtained in CH3CN using polymerization charges between 0.1 and 1 mC.

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3.2. Metal Binding Properties of Monomer L in Homogeneous Phase Firstly, the metal ion binding properties of monomer L were clearly demonstrated by electrochemical experiments and mass spectrometry analyses. The addition of L to Cu(II) or Hg(II) buffered solutions resulted in significant shifts of the metal based CV reduction peaks towards more negative potential, i.e., from Epc 0.09 to 0.26 V for Cu(II), and from Epc 0.15 V to 1.3 V for Hg(II) (Fig. 1). The anodic stripping peaks potentials were conversely weakly affected by the complexation processes, although the peaks intensities were strongly depressed. The affinity of L towards copper and mercury ions has been further confirmed by mass spectrometry/electrospray (ES-MS) experiments. ES-MS spectra recorded for equimolar aqueous solutions of Cu(II) ions and L (1 mg L1 in 1 : 1 CH3CN:H2O solutions) indeed displayed signals attributed to [(L-H)Cu] (m/z 778.4 (100%)) and [(L-3H)Cu2] (m/z 841.4 (100%)). Evidences for the formation of 1 : 1 and 1 : 2 complexes between L and Hg(II) were also observed in similar conditions, as proved by signals at m/z 917.6 (100%) attributed to [LHg-H] and 1114.5 (100%) corresponding to [(L-3H)Hg2]. These results clearly highlight the efficient metal binding properties of the EDTA-like monomer L featuring two amine and four amide coordinating groups. Such neutral ligand has been recently shown to be fully suited for the complexation of numerous metallic species to form monometallic octahedral complexes wherein both amines and four carbonyl functions are tightly bound to one divalent metal ion [66 68]. The observation of signals whose mass correspond to partially deprotonated ligand is moreover in full agreement with previously reported speciation studies showing that such amide functions might be anionic at high pH values [68].

Fig. 1. Cyclic voltammograms at a bare carbon disk electrode (3 mm diameter) recorded in acetate buffer (pH 5.5; 0.1 mol L1) containing A) 5 104 mol L1 Cu(OAc)2 and B) 5 104 mol L1 Hg(OAc)2, without (dashed curve) and with (full line) monomer L 5 104 M; v 25 mV s1.

3.3. Sensing Properties of C j polyL Towards Mercury and Copper Ions The complexing properties of C j polyL electrodes were investigated using the chemical preconcentration-anodic
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stripping method [27]. Dipping the modified electrodes into aqueous 0.1 mol L1 acetate buffer solutions containing a given metal cation led to the complexation of metal ions within the polymer films (chemical accumulation at open circuit). After the pre-concentration step the modified electrode was carefully rinsed with water in order to remove unbounded metal ions, and transferred into a metal-free acetate buffer in which the collected metal ions were reduced to zerovalent metal, before recording the corresponding stripping currents using differential pulse voltammetry. Typical DPV curves obtained after 10-min of preconcentration in 105 mol L1 solutions of Hg(II) or Cu(II) acetate exhibited stripping peaks around 0.1 Vand 0.3 V (vs. Ag j AgCl) corresponding to the oxidationdissolution of the electroprecipitated metals (Fig. 2). The effect of pH, preconcentration time, deposition potential, and deposition time on the electrodes sensing properties was carefully investigated. The stripping current was especially measured upon changing the pH of the accumulation solution from pH 3.4 to 6.9 (Cu(II) solutions), and from pH 3.5 to 5.5 (Hg(II) solutions). These investigations were conducted at room temperature in the same other conditions, i.e., 5 104 mol L1 in metal ions, complexation and reduction times of 10 min, and using film modified electrodes synthesized with polymerization charges of 0.5 mC (GL 7 109 mol cm2). The electrochemical responses were clearly influenced by the pH, and the stripping peaks reached a maximum value at pH 4.5 for
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Voltammetric Sensing of Mercury and Copper Cations

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Fig. 2. DPV curves recorded at C j polyL electrodes (GL 7 109 mol cm2) in 0.1 mol L1 aqueous acetate buffer (pH 5.5 for Cu, and 4.5 for Hg) after 10-min preconcentration in 105 mol L1 Hg(OAc)2 (full line) and Cu(OAc)2 (dashed line) buffered solutions; electroprecipitation to zerovalent metal was performed at 1.8 V (Hg2 ! Hg0) and 0.9 V (Cu2 ! Cu0) for 10 min in metal-free electrolyte.

mercury and pH 5.5 for copper. The pH of the preconcentration solutions was therefore set to 5.5 and 4.5 in all experiments involving Cu(II) and Hg(II) ions, respectively. The influence of the reduction potential on the anodic stripping peak currents was examined over the potential range of 0.45 V to 0.9 V with copper ions, and from 1.4 to 1.8 V for mercury ions. We found that reduction potentials of 0.9 V and 1.8 V were sufficient, in our experimental conditions, to fully reduce all entrapped Cu(II) and Hg(II) species, respectively. The effect of preconcentration time was studied in the range 1 min to 10 min for copper, and between 1 min to 60 min for mercury. The accumulation solutions were 0.1 mol L1 acetate buffer 5 104 mol L1 in metal ions, at pH 4.5 for mercury and pH 5.5 for copper. The stripping peak currents happened to exponentially increase with preconcentration time until reaching a constant current level, attributed to the complexation of almost all the accessible complexing sites in the polyL films. Peak currents were found to be constant (96% of max. current) after 10 min of preconcentration in the copper solutions, and after 20 min in the mercury solutions (Fig. 3). The effect of incorporation time is clearly related to the nature of the metallic species featuring different complexation and/or through film-diffusion kinetics. Such result brings out another important benefit of using chemically modified electrodes, which is the opportunity to potentially discriminate metallic species taking advantage of incorporation kinetics. The effect of deposition time of metallic mercury and copper into C j polyL by electroreduction of the complexed metal cations was investigated in the 1 min to 10 min time range. Modified electrodes were immersed in buffered 103 mol L1 solutions of copper ions, or 5 104 mol L1 solutions of mercury ions. Reductions were conducted at 0.9 V for copper and 1.8 V for mercury ions. Surprisingly, the mercury stripping peak currents increased with deposition time from 1 to 3 min and decreased for longer reduction times (Fig. 3). This unexpected behavior might be
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Fig. 3. Anodic stripping peak currents vs. the accumulation time in C j polyL (GL 7 109 mol cm2) film modified electrodes. A) Accumulation in 103 mol L1 Cu(II) (acetate buffer; pH 5.5); deposition of metal was at 0.9 V. B) Accumulation in 5 104 mol L1 Hg(II) (acetate buffer; pH 4.5); deposition of metal was at 1.8 V.

attributed to partial loss of metallic mercury from the electrode surface into the solution in the course of the reduction. For copper ions the peak current increase from 1 to 5 min of electroreduction to reach a plateau (Fig. 4). To ensure a complete reduction of copper and mercury ions, reduction times of 10 min and 3 min, respectively, were chosen for all experiments. Then, using the best experimental conditions previously found (pH, preconcentration time, deposition potential and deposition time), the C j polyL modified electrodes have been used to determine concentrations of Cu(II) and Hg(II) ions in aqueous media, using the chemical preconcentration-anodic stripping method. DPV signals were recorded for various concentrations of metal ions using a freshly prepared electrode for each measurement. With C j polyL of GL % 7 109 mol cm2, linear calibration plots were obtained in the concentration range from 108 to 8 106 mol L1 for Hg(II) (Fig. 5) and 5 108 to 105 mol L1 for Cu(II), with correlation coefficients of 0.997 and 0.991 for mercury and copper, respectively. Using a preconcentration time of 10 min and C j polyL with GL 7 109 mol cm2, the detection limits were estimated at 5 108 mol L1 for Cu (II) and 108 mol L1 for Hg (II). As expected, increasing the film thickness and, thus the number of complexing sites, resulted in larger stripping currents. It needs to be stressed out that Cu(II) calibration plots recorded at C j polyL with two different film thickness
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Fig. 4. Effect of time of electroreduction of the complexed metal ions into C j polyL (GL 7 109 mol cm2) modified electrodes on the anodic stripping peak currents. A) Accumulation for 20 min in 5 104 mol L1 Hg(OAc)2 in acetate buffer (pH 4.5); reduction was at 1.8 V. B) Accumulation for 10 min in 103 mol L1 Cu(OAc)2 in acetate buffer (pH 5.5); reduction was at 0.9 V.

Fig. 5. A) DPV peak currents recorded at different C j polyL electrodes (&, GL % 7 109 mol cm2; *, GL % 108 mol cm2) as a function of Hg(II) concentration in the accumulation solution (acetate buffer, pH 4.5, accumulation time 20 min, reduction for 3 min at 1.8 V). B) Linear parts of the calibration plots.

showed almost identical linear parts, although a better detection limit for copper (108 mol L1) was found with thicker polymer films (GL % 108 mol cm2). However the detection limit for Hg(II) ions was not improved by increasing the polymer thickness. What unambiguously come out from the latter curves is that the electrochemical response is much larger, and consequently the detection limits much lower, with mercury than with copper. These highly promising results are logically related to the ability of the 3D-polymer to incorporate larger amounts of mercury ions due to specific structural features promoting such ligand/Hg(II) interactions.

3.4. Reproducibility and Precision of Measurements The reproducibility of Cu(II) analyses was examined with five identical C j polyL electrodes modified by electropolymerization in a 103 mol L1 solution of monomer L (charge passed 0.5 mC). Each modified electrode was dipped for 10 min into a 5 104 mol L1 Cu(II) solution. The corresponding stripping currents were in the range 2.9 to 3.7 mA, which shows that the reproducibility is higher than 90% in both preparation and sensing processes. Moreover, 10 consecutive analyses of copper carried out in 5 104 mol L1 accumulation solutions, followed by 6
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analyses of 2 105 mol L1 solutions of Cu(II), were performed using the same modified electrode, giving relative standard deviation of 9.4% and 11.1%, respectively. After each determination of copper regeneration of the metal free C j polyL electrode was achieved by soaking the electrode for 3 min in a 103 mol L1 EDTA aqueous solution, followed by careful rinsing. This result clearly brings out that C j polyL analytical electrodes can potentially be used for multiple measurements. A similar investigation was conducted with mercury(II) solutions. We found that this ion remains more strongly complexed into polyL than Cu(II) cations. EDTA has no major effect on mercury decomplexation, even using concentrations up to 102 mol L1. The effective regeneration of mercury-free films required soaking complexed electrodes for longer times (15 min) in 102 mol L1 solutions of sodium diethyldithiocarbamate (DEDTC). It needs however to be stressed out that the C j polyL electrodes were significantly affected by the treatment with DEDTC, as proved by a gradual loss of the complexing properties and sensitivity on repeated regeneration treatments. For instance ten consecutive determinations of mercury using the same modified electrode gave a relative standard deviation of 12.5%. This result contrasts with the fact that 10 measurements carried out in 5 104 mol L1 Hg(II) solutions using 10 freshly prepared C j polyL electrodes of similar size, led conversely to a much lower standard deviation of 3.8%.
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This investigation thus clearly shows that C j polyLbased analytical measurements are much more reproducible with mercury than with copper ions. However the strong interactions between mercury and the EDTA-like polymer compel the use of rather concentrated DEDTC for the regeneration of metal-free film. This treatment greatly limits the long term operating stability of the modified electrodes, and precludes their repeated use for mercury sensing. However the good reproducibility of the elaboration process should allow circumventing this problem.
Fig. 6. DPV curves recorded at a C j polyL (GL % 7 109 mol cm2) in acetate buffer (pH 4.5) after soaking the electrodes for 20 min in acetate buffer containing Hg(OAc)2 at 106 mol L1 (dotted line); Cu(OAc)2, Cd(NO3)2, Pb(NO3)2, Hg(OAc)2 at 106 mol L1 (dashed line); Cu(OAc)2, Cd(NO3)2, Pb(NO3)2 at 104 mol L1, and Hg(OAc)2 at 106 mol L1 (full line). Reduction of complexed metal ions was performed in acetate buffer (pH 4.5) at 1.8 V for 3 min.

3.5. Selectivity and Interference Effects Firstly, the selectivity of the polyL films towards mercury ions was assessed by soaking a C j polyL electrode for 20 min in acetate buffer (pH 4.5) containing a mixture of Hg(II), Cu(II), Pb(II) and Cd(II) at the same concentration (106 mol L1). After careful rinsing and reduction at 1.8 V for 3 min, metal species entrapped in the polyL modified film were readily identified through DPV stripping analysis conducted in a metal free electrolyte (acetate buffer, pH 4.5). It should be emphasized that the DPV curve obtained (Fig. 6, dashed line) is very similar to that observed after preconcentration in a solution containing only mercury species (Fig. 6, dotted line). A unique anodic stripping peak was observed at about 0.25 V, attributed to the oxidation of encapsulated metallic mercury. The absence of signals that could be attributed to the stripping of any other metal clearly demonstrates the selectivity of polyL towards Hg(II) species complexation in these experimental conditions. Cu(II), Pb(II) and Cd(II) ions were however entrapped in the complexing polymer and thus observed on stripping DPV voltammograms as their concentrations in the accumulation solution were increased up to 104 mol L1, while that of Hg(II) was kept at 106 mol L1 (Fig. 6, plain line). It should be noted that the drop in the mercury stripping peak current was lower than 10% as the concentration in competing cations was 100 times that of mercury. To accurately estimate the selectivity of C j polyL for Hg(II) over Cu(II) ions, stripping analyses were conducted with modified electrodes immersed in solutions containing 5 106 mol L1 Hg(II) and increasing concentrations of Cu(II) ions from 5 106 to 5 104 mol L1. The column chart shown on Figure 7 clearly shows that the copper-based stripping signal appears as [Cu(II)]/[Hg(II)] ! 10, and that Hg(II) stripping currents largely prevail even with hundredfold larger Cu(II) concentrations in the accumulation solution. Changes in stripping peak currents as a function of the [Cu(II)]/[Hg(II)] ratio in the accumulation solution reveal the significant selectivity of the C j polyL electrode towards mercury. Even in presence of a large excess of copper, the intensity of the mercury based signal remains roughly constant. This behavior suggests that the incorporation of copper is not made at the expense of mercury, which does not occupy all available binding sites in the polymer.
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Fig. 7. Evolution of Hg and Cu stripping currents as a function of the [Cu(II)]/[Hg(II)] ratio in the preconcentration solution; stripping currents were recorded by DPV at C j polyL (GL % 7 109 mol cm2) modified electrodes in acetate buffer (pH 4.5), after soaking the electrodes for 20 min in acetate buffer containing Hg(OAc)2 at 5 106 mol L1 and increasing concentrations of Cu(OAc)2 (from 5 106 to 5 104 mol L1); reduction of metal ions was performed in acetate buffer (pH 4.5) at 1.8 V for 3 min.

The greater affinity of polyL to mercury in the presence of copper cations was further confirmed in a separate experiment, through the observation of equivalent copper and mercury based stripping signals recorded with a C j polyL electrode dipped in a solution containing more than a thousand-fold excess of copper cations (5 104 mol L1, against 4 107 mol L1 for Hg(II) cations), at pH 5.5.

3.6. Imprinted C j polyL Electrodes A feature of interest in the monomer structure arises from the presence of four polymerizable pyrrole moieties. In contrast to the vast majority of 1D-polymers grown from building block bearing one single pyrrole, this specific
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84 property was thought to improve the cation binding selectivity through an enhanced rigidity and controlled dimensionality of the polymeric material. We especially investigated the imprinting properties of such 3D-molecular architectures upon polymerizing monomers in presence of metal ions and analyzing the effects of such imprinting approach on the analytic responses of C j polyL. In a typical experiment, the oxidative electropolymerization of L was performed at 0.85 V in the presence of a given metal ion (Hg(II), Cu(II), Zn (II)). Imprinting ions were then removed from the polymer upon soaking the modified electrodes in sodium dithiocarbamate or EDTA solutions, and the decomplexation was checked by DPV in the potential range of anodic stripping corresponding to the given metal. The analytic properties of these C j polyL electrodes were then investigated using the same procedures as those described in the previous sections. In order to try to improve the sensitivity towards Hg(II) ions, the electropolymerization of L was performed acetonitrile 0.1 mol L1 TBAP electrolyte containing 103 mol L1 L and one molar equivalent of mercury acetate. The resulting modified electrode (GL 108 mol cm2) was then immersed in aqueous sodium diethyldithiocarbamate (102 mol L1) for 20 min under stirring, to yield a metal-free imprinted polyL film. It is noteworthy that this overall treatment turned out to significantly improve the Hg(II) detection limit, down to 5 1010 mol L1. However, as above-mentioned, the C j polyL electrodes are significantly affected by the treatment with sodium diethyldithiocarbamate, leading to a gradual loss of the complexing properties and sensitivity on repeated use. The electrosynthesis of imprinted polymer films has also been evaluated in the presence of copper cations. The electropolymerization of L performed the presence of copper acetate (0.3 to 5 molar equivalents) was poorly efficient. This behavior was attributed to the strong oxidizing properties of the copper-acetonitrile complex, leading to a chemical oxidation of L and to a fast degradation of the polymerization solution [69]. However thin polymer films could be obtained in these experimental conditions and, after removing the copper species complexed in the imprinted polymer film by soaking in EDTA solution, the sensing properties towards Cu(II) of the copper-imprinted C j polyL electrodes were then evaluated in a 5 104 M Cu(OAc)2 solution. This simple test procedure readily showed that the use of imprinting copper does not improve the analytic response towards these cations, since the results obtained were similar to that already found using nonimprinted polymer film modified electrodes. To avoid a metal-driven oxidation and degradation of the polymerization solution, and to electrosynthesize imprinted polymer film with metal cation easier to remove than mercury species, C j polyL were elaborated in the presence of Zn(II) as its trifluoromethanesulfonate salt. The electropolymerization of L (103 mol L1) was thus performed in the presence of four molar equivalents of Zn(II), in acetonitrile containing 0.1 mol L1 TBAP. Then the imprinting ions were subsequently removed by immersion of
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Fig. 8. DPV peak currents for copper stripping recorded at (*) C j polyL electrodes (GL % 7 109 mol cm2) and (~) Zn-imprinted C j polyL electrodes (GL % 6.8 109 mol cm2) as a function of Cu(OAc)2 concentration in the accumulation solution (acetate buffer, pH 5.5; preconcentration for 10 min; reduction of metal ions at 0.9 V for 10 min. Inset: linear parts of the calibration plots.

C j polyL in a stirred EDTA solution (102 mol L1) for 3 minutes. The modified electrodes prepared in this way have been used for Cu(II) sensing, and the imprinting effect is clearly revealed on Figure 8 showing the intensity of copper-based anodic stripping currents recorded with imprinted and nonimprinted C j polyL electrodes. As a matter of fact the Zn-imprinted electrodes (GL % 6.8 109 mol cm2) exhibit an improved detection limit of 5 1010 mol L1, to be compared to the 108 mol L1 limit reached with nonimprinted electrodes (GL % 7 109 mol cm2), as well as a lower uptake for larger copper ions concentrations. A linear calibration plot could be obtained using imprinted C j polyL (GL % 6.8 109 mol cm2) with Cu(II) concentrations ranging from 2 109 to 3 106 mol L1. It needs to be stressed out that this linear range is smaller than that obtained with nonimprinted electrodes.

4. Conclusions
It is well recognized that the most efficient approach towards chelating-modified electrodes is the direct electropolymerization of complexing monomers, producing in one step stable functionalized polymers films with controlled sizes and sites concentrations. This straight forward approach towards analytic materials has however rarely been applied for the determination of trace metals in aqueous media. In the present article, we have shown that carbon electrodes modified by electropolymerization of a tetra pyrrole appended EDTA-like derivative can be used to achieve an efficient electroanalytical sensing of metal cations. The metal binding properties of this novel chelating building block have been demonstrated in homogeneous media and the analytical response of the related modified electrodes C j polyL have been thoroughly investigated by electrochemical methods. This poly(EDTA-like) electrode material especially showed a great affinity towards Hg(II)
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ions against Cu(II) ions, while being almost insensitive to Cd(II) and Pb(II) cations. In contrast to the vast majority of 1D-polymers grown from building block bearing one single polymerizable moiety, the presence of four pyrrole groups per monomer leads to networked architectures with enhanced rigidity and dimensionality. We especially investigated the imprinting properties of such 3D-molecular architectures upon polymerizing the dendronic EDTA monomer in presence of metal ions and analyzing the effects of such imprinting on the analytic responses of C j polyL. Imprinted electrodes especially led to significantly improved Hg(II) detection limit of 5 1010 mol L1, to be compared to the 108 mol L1 limit determined without imprinting effect. These results not only further demonstrate the great potential of chemically modified electrodes in analytic chemistry, they also open novel perspectives to achieve selective cation sensing though the templated growth of three dimensional complexing networks.

5. Acknowledgements
This work was partly financially supported by the Associ ation Universitaire de la Francophonie (Projet de cooperation scientifique inter-universitaire, cod 6316PS545/ 23.02.2005).

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