Sensors and Actuators B 147 (2010) 191197

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Sensors and Actuators B: Chemical

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

Poly[meso-tetrakis(2-thienyl)porphyrin] for the sensitive electrochemical detection of explosives

Wei Chen a , Ying Wang a , Christian Brckner b , Chang Ming Li c , Yu Lei a,
a b c

Department of Chemical, Materials and Biomolecular Engineering, University of Connecticut, 191 Auditorium Rd, Storrs, CT 06269, USA Department of Chemistry, University of Connecticut, Storrs, CT 06269, USA School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 637457, Singapore

a r t i c l e

i n f o

a b s t r a c t
Poly[meso-tetrakis(2-thienyl)porphyrin] (pTTP) was prepared through electrochemical polymerization of meso-tetrakis(2-thienyl)porphyrin (TTP). The pTTP lm thus generated was characterized by cyclic voltammetry (CV), SEM, and Raman spectroscopy. The ability of the pTTP-modied electrode for the detection of a range of explosives in aqueous solution was investigated using differential pulse voltammetry (DPV). The results demonstrate that pTTP lm greatly enhances the reduction of 2,4-DNT, TNT, Tetryl, RDX, and nitromethane when compared to an unmodied electrode, a TTP-modied electrode, or a polythiophene-modied electrode. This may be attributed to the high afnity of the porphyrin ring in the pTTP conducting chain to the nitrocompound and the resulting enhanced electron transfer during the explosives reduction. Under optimized conditions, the pTTP-modied electrode shows a limit of detection (S/N = 3) as low as 8 ppb for 2,4-DNT and TNT, 9 ppb of Tetryl, 96 ppb of RDX, and 43 ppb of nitromethane without requiring any sample pre-concentration step. This study indicates that pTTP can serve as a new class of material in the electrochemical detection of explosives. 2010 Elsevier B.V. All rights reserved.

Article history: Received 7 November 2009 Received in revised form 11 March 2010 Accepted 12 March 2010 Available online 17 March 2010 Keywords: pTTP Differential pulse voltammetry Explosive detection Nitroalkane Nitroaromatic compound

1. Introduction 2,4-Dinitrotoluene (2,4-DNT), 2,4,6-trinitrotoluene (TNT), cyclotrimethylenetrinitramine (RDX), and trinitrophenyl-Nmethylnitramine (Tetryl) are today the most commonly used explosives (Scheme 1 ) [1]. Their production and wide military and civil uses have lead to severe contamination of the water system [2]. All the explosives are known toxins to humans [3]. This circumstance alone demands their efcient detection in aqueous environment, and this public health challenge has received considerable attention [4]. In addition, terrorism has emerged as a threat to public safety throughout the world. The most common form of terrorism uses conventional explosives and has cost the lives of far more people than biological, chemical or radioactive threat substances combined have claimed, though the latter are generally on the forefront of the public mind. The extension of terrorism activities from land to marine environments has also elevated the priority of the detection of explosives in aqueous environment [5,6]. Nitromethane has also been used in the preparation of home-made explosives. This liquid is readily acquired as it is used as a fuel or fuel-additive in certain motor sports. Nitromethane

Corresponding author. E-mail address: ylei@engr.uconn.edu (Y. Lei). 0925-4005/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.snb.2010.03.046

is in fact a more energetic high explosive than TNT, although the latter is characterized by a higher velocity of detonation and higher brisance. Thus, the detection of nitromethane is also extremely important. In the past decades, a number of technologies were developed for the detection of explosives in aqueous samples. The approved standard technology for trace explosive detection is the US EPA protocol SW-846 Method 8330 involving reverse-phase HPLC with UV detection [7]. Others reported methods include chemiluminescence [8,9], spectrophotometric assays [10,11], the use of immunosensors [1216], and surface enhanced Raman scattering [17]. However, electrochemical methods, owing to their relatively low cost, efciency, high sensitivity, and ease of operation, have emerged as preferable for the detection of commercial and home-made explosives [1,5,18]. Various electrochemical methods, such as anodic stripping voltammetry, square wave voltammetry, cyclic voltammetry, and amperometry, have been extensively explored in the detection of explosives [1,3,6,1824]. In addition, a range of electrode materials, such as carbon nanotubes [18], carbon nanotube-metallic nanoparticle composites [25], core-shell tincarbon [26], and boron doped diamond [20], have been used to enhance the electrochemical reduction wave, thereby increasing the sensitivity of the electrochemical detection of explosives. Even though many of these systems and materials are functional or even elegant, many do not lend themselves to large scale production, are

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chemical polymerization of TTP onto glassy carbon (GC) electrodes (dia. 3 mm). 2.2. Apparatus The cyclic voltammetric (CV) deposition of pTTP and differential pulse voltammetric measurements were performed using an electrochemical workstation (Bio-logic VMP3) with a conventional three-electrode conguration, including a working electrode (bare or modied GC electrode), an Ag/AgCl reference electrode, and a platinum counter electrode. Before each experiment, the solution was purged with compressed nitrogen for 15 min. The morphology of the electropolymerized pTTP lm was characterized using JEOL 6335F Field Emission Scanning Electron Microscope (FESEM). The Raman spectra were recorded on a Renishaw Ramascope Micro-Raman with 512 nm wavelength laser to investigate the bond stretching of the as-prepared pTTP lm and the TTP monomer.
Scheme 1. Chemical structures of analytes.

2.3. Electrochemical deposition of pTTP costly, have short lifetimes, or have other practical disadvantages. Therefore, new and improved materials and methods for explosives sensing are still in great demand. Porphyrins are tetrapyrrolic, aromatic macrocycles. The most characteristic property of porphyrins is their large aromatic systems that are at the origin of their deep coloration, their distinctive electronic spectra, and their photo- and electrochemical activity. A wide range of naturally occurring and synthetic porphyrins are available. Porphyrins and their metal complexes (metalloporphyrins) have attracted considerable attention as electrocatalyst for reduction and oxidation processes [2731]. Electron-decient analytes, such as nitroaromatic compounds, have a natural afnity to electron-rich porphyrins. This interaction perturbs the porphyrin -system. This, in turn, is reected in their altered electronic properties. Thus, the porphyrin-explosives interaction has become the basis for the uorescence detection of nitroaromatic explosives [3235]. To incorporate the explosives afnity of porphyrins and their electrocatalytic property within polythiophene, we envisioned that the known thiophenederivatized porphyrin meso-tetrakis(2-thienyl)porphyrin (TTP) can be polymerized to provide a conducting polymer that incorporates porphyrin moieties in its conductive chains [36]. We will report here that, indeed, TTP can be electropolymerized as a lm onto an electrode, and that the resulting polymer lm-modied electrode exhibits enhanced electrocatalytic properties when compared to polythiophene-coated, TTP-coated, or untreated electrodes. The coating can be exploited for the sensitive detection of explosives in aqueous solution using differential pulse voltammetry (DPV). 2. Materials and methods 2.1. Chemicals meso-Tetrakis(2-thienyl)porphyrin (TTP) was synthesized using known procedures [36,37]. Tetrabutylammonium hexauorophosphate (TBAPF6 ), thiophene, DNT, and nitromethane were purchased from Aldrich, dichloromethane (CH2 Cl2 ) and sodium phosphate monobasic monohydrate (NaH2 PO4 H2 O) from Acros, and anhydrous dibasic sodium phosphate (Na2 HPO4 ) from Fisher Scientic. The standard solutions of TNT, Tetryl, and RDX in acetonitrile (all 1000 g/mL) were purchased from Supelco (Bellefonte, PA), Ultra Scientic (North Kingstown, RI), and Chem Service (Westchester, PA), respectively. Conductive ITO glass slides (50100 /sq) were obtained from Nanocs (New York, NY). Dichloromethane was used as solvent with TBAPF6 as supporting electrolyte for the electroAll electrochemical experiments were carried out in an electrochemical cell with a working volume of 5 mL at room temperature. Before electrochemical polymerization of TTP, the GC electrode was polished sequentially with ne-grade alumina powders (1, 0.3, and 0.05 m) to obtain a smooth and shining surface. The electrochemical deposition of pTTP lms was carried out by cyclic voltammetry (02.0 V at 20 mV/s). The electrolyte consisted of 1 mM TTP monomer and 0.1 M TBAPF6 in CH2 Cl2 . After the electropolymerization, the pTTP-coated GC electrode was washed with CH2 Cl2 to remove any non-polymerized TTP. For SEM and Raman investigation, pTTP lms were deposited on a small piece of conductive ITO glass under the same conditions. 2.4. Electrochemical detection of explosive compounds The detection of explosives (2,4-DNT, TNT, Tetryl, RDX, and nitromethane) was performed by differential pulse voltammetry in 0.01 M pH 7.0 phosphate buffer solution. Prior to the measurements, the solution was purged with compressed high purity N2 for 15 min, and a gentle N2 stream was maintained over the solution during the measurements. The differential pulse voltammetry was recorded using the optimized DPV parameters, 50 mV pulse height, 250 ms pulse width, 5 mV step height, and 500 ms step time. 3. Results and discussion 3.1. Electrochemical synthesis of pTTP Repetitive cyclic voltammetry scans of a TTP monomer (1 mM) and TBAPF6 (0.1 M) in CH2 Cl2 solution provide clear indications for an electrochemical polymerization and growths of a pTTP conducting lm on the GC electrode. In the rst two cycles (Fig. 1, inset), there are three anodic peaks. Their origin is not clear at current stage, but tentatively attributed to the oxidation of the porphyrin, the meso-2-thienyl groups, and/or the trace amounts of impurities present in the meso-tetrakis(2-thienyl)porphyrin. After the rst four cycles, the electrode is stabilized and the oxidation and reduction currents increase regularly, indicative of the growth of a conducting pTTP layer. The anodic peak at ca. +0.73 V can be assigned to the oxidation of the porphyrin ring [38], while the continuous increase of the oxidation current above +1.2 V with the increase of scanning cycles can be attributed to the successive oxidation of meso-2-thienyl groups and the deposition of conducting pTTP lm on the GC electrode.

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Fig. 1. Cyclic voltammogram of the pTTP lm growth (after the rst four cycles). The inset shows the rst four CV cycles. Electrolyte: 1 mM TTP and 0.1 M TBAPF6 in CH2 Cl2 . Scan rate = 20 mV/s.

Fig. 2. Raman spectra of TTP and pTTP on ITO glass. Excitation wavelength = 512 nm.

3.2. Raman and SEM characterizations of the pTTP lm Scheme 2 shows the proposed constitution of the pTTP lm. Note that in TTP, one -position in each of the four thiophenes per TTP is unsubstituted. Based on the known reactivity of thiophene and the constitution of polythiophene, this position is the most likely position to be linked to other thiophene units during an electrochemical polymerization. However, the insolubility of the polymer lm and its thinness will not allow the direct probing of the nature of the polymer linkage by, for instance, NMR spectroscopy, but Raman spectroscopic evidence provides clear indications of the connectivity of the polymer. To compare the bond stretches within the pTTP lm with those of the TTP monomer, we used Raman spectroscopy. Fig. 2 shows the Raman spectra of TTP and pTTP (grown on an ITO electrode). Both display some diagnostic bands corresponding to vibrations of porphyrin macrocycle (970, 1242 and 1367 cm1 for pTTP and 1000, 1240, 1370, 1448 and 1555 cm1 for TTP) [39]. However, several characteristic Raman peaks in the range of 590800 cm1 are observed for pTTP, while they are absent in the TTP monomer. Specically, the peak at 705 cm1 for pTTP, which is diagnostic for the CSC ring deformation mode in polymerized thienyl groups [40], is absent in the spectrum of monomeric TTP monomers, but clearly present in pTTP, thus indicating that polymerization, as predicted, had taken place via the -positions of the thienyl groups. The surface morphology of a pTTP lm deposited on an ITO electrode was investigated by scanning electron microscopy

(SEM). Fig. 3 shows the comparison of representative SEM images of the bare ITO glass and the pTTP lm. While the bare ITO glass possesses a clean and smooth surface, the pTTP lm is clearly visible and exhibits a dense morphology. Unlike the surface morphology of conventional conducting polymers such as polypyrrole that show typical granular morphology [41,42], the surface of pTTP lm is relatively smooth. Perhaps this is due to the fact that ideally TTP is polymerized along all four meso-thienyl groups, forming a 2-dimensional lattice [43]. The thickness of the layer after three voltammetric cycles was 120 nm. 3.3. Voltammetric studies of 2,4-DNT on the pTTP-modied GC electrode To test the voltammetric reduction of explosives on the pTTPmodied GC electrode, 2,4-DNT was used as the rst target. Fig. 4a shows the reduction peak region of the CV resulting from the presence of 100 ppb 2,4-DNT using a bare GC electrode and a pTTPmodied GC electrode in 0.01 M pH 7 phosphate buffer at a scan rate of 50 mV/s. One can see that the reduction of 2,4-DNT on the pTTP-coated GC electrode shows two well-dened reduction peaks (peak I and peak II). In comparison, the reduction of 2,4-DNT on the bare GC electrode is barely noticeable, demonstrating that the pTTP coating can greatly enhance the electrochemical reduction of 2,4DNT. To answer the question whether it is the polythiophene phase or the porphyrin of the pTTP coating that is responsible for the electrocatalysis, we prepared a polythiophene-modied GC electrode and a TTP-modied GC electrode. Both modied electrodes

Scheme 2. Electrochemical polymerization of TTP.

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Fig. 3. Typical SEM images of (a) a bare ITO glass and (b) pTTP lm on ITO glass.

show a performance that is very similar to that of the bare electrode (Fig. 6), highlighting the crucial role the porphyrins incorporated in the conducting chain play in the reduction of 2,4-DNT. The electrochemical reduction of nitroaromatic compounds is well understood [3,19,20,24]. Each peak corresponds to the sequential reduction of one nitro group to generate hydroxylamines, followed by a total or partial reduction of the latter to amine groups (Eqs. (1) and (2)). -NO2 + 4e + 4H+ -NHOH + 2e + 2H
+

-NHOH + H2 O - NH2 + H2 O

(1) (2)

Prophyrins are electron-rich, while the 2,4-DNT is electron decient due to the strong electron-withdrawing power of the two nitro groups. Therefore, the basis for a favorable interaction between the pTTP and DNT, possibly enhanced by a charge-transfer component, are given. The resulting close contact of 2,4-DNT with the conducting pTTP lm enhances its electrochemical reduction. The CV curves of the pTTP-modied GC electrode in 0.01 M pH 7.0 phosphate buffer containing 100 ppb 2,4-DNT were also recorded at various scan rates ( ). The peak currents were plotted as a function of the square root of the scan rate ( 1/2 ). As shown in Fig. 4b, both of the reduction peak currents are proportional to 1/2 , showing that the reduction of 2,4-DNT on the pTTP-modied electrode is a typical diffusion controlled electrochemical event. The effect of pH on the reduction of 2,4-DNT is shown in Fig. 4c. A negative shift of reduction peak potential was observed with the increase of the buffer pH values. A slope of 48.3 and 44.1 mV/pH was obtained for reduction peaks I and II, respectively, indicating that the mechanism of both reduction processes involve approximately the same number of electrons and protons. This nding is consistent with the reductions along Eqs. (1) and (2), and is also consistent with other reports [3,19,20,26]. 3.4. 2,4-DNT detection on the pTTP-modied GC electrode The detection of 2,4-DNT using DPV was optimized with respect to the CV deposition cycles of pTTP and the buffer pH value. The thickness of the pTTP lm is controlled by the number of CV deposition cycles: the larger of the number of CV deposition cycles, the thicker the deposited pTTP lm. Fig. 5a shows the effect of the CV deposition cycles on the response to 1 ppm 2,4-DNT in buffer. The background-subtracted reduction peak current at peak I was recorded here. As expected, the response increased initially but reached a maximum at three cycles of CV deposition. More deposition cycles lead to a gradual signal decrease. The initial increase is attributed to an enhanced catalytic activity and electron transfer of the deposited pTTP, while the decrease at higher numbers of CV deposition cycles is likely due to increased mass and electron transport resistance caused by the rigid and thicker pTTP lm. Thus three CV deposition cycles were applied for the preparation of the pTTP-modied electrodes used in subsequent work.

Fig. 4. (a) Cyclic voltammograms (the reduction peaks region) at the bare GC electrode (dash line) and the pTTP-modied GC electrode (solid line) for 100 ppb 2,4-DNT in 0.01 M pH 7.0 phosphate buffer. Scan rate = 100 mV/s. (b) The reduction peak currents of 100 ppb 2,4-DNT in 0.01 M pH 7.0 phosphate buffer versus the square root of scan rate for the reduction peak I () and II ( ), respectively. (c) The pH dependence of the peak potentials in 2,4-DNT reduction for the reduction peak I () and II ( ), respectively.

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Fig. 6. The calibration plots for 2,4-DNT on the pTTP-modied electrode ( ), the bare GC electrode (), the drop-cast TTP-modied GC electrode ( ), and the polythiophene-modied GC electrode ( ). The current responses based on the reduction peak I are the values after background-subtraction. The inset displays the differential pulse voltammograms at the pTTP-modied GC electrode for increasing levels of 2,4-DNT in steps of 50 ppb.

Fig. 5. Optimization of 2,4-DNT reduction at the pTTP-modied GC electrode with respect to (a) the deposition cycles of pTTP lm and (b) the buffer pH. The concentration of 2,4-DNT is 1 ppm. The reduction peak I was used here.

subtraction, used to construct a calibration curve, presented in Fig. 6. The response of the pTTP-modied GC electrode increases with the analyte concentration but gradually levels off at a concentration above 250 ppb showing an expected saturation response. The limit of detection (LOD) was estimated to be 8 ppb 2,4-DNT (signal-to-noise ratio of 3). To demonstrate the activity of the pTTP-modied GC electrode, a comparison to three electrodes was made: (1) a bare GC electrode, (2) a GC electrode upon which TTP monomer was drop-deposited, and (3) a polythiophene-modied GC electrode. Fig. 6 shows the results. Compared to the response of the pTTP-modied GC electrode upon the increase of DNT, much smaller responses were recorded for all other electrodes. These results indicate that pTTP can signicantly enhance the reduction of 2,4-DNT.

As the reduction of 2,4-DNT consumes protons (Eqs. (1) and (2)), the effect of pH on the response was also investigated to establish the optimal assay pH value. As shown in Fig. 5b, the optimal pH value for the assay is at pH 5.9. The electrochemical signal strength of the reduction of 2,4-DNT decreases only slightly with a drop of pH but falls off sharply at pH values above of 7.0. Thus, as expected, high proton concentration generally favors the reduction of 2,4-DNT, and the reduction is greatly inhibited in basic solution. However, when the pH value is lower than the optimal pH, the reduction of 2,4-DNT is slightly suppressed. This can be understood considering that a too low pH solution may protonate the free base of porphyrin in the pTTP lm [44], thus changing the charge status of the porphyrin and weakening its binding afnity to 2,4-DNT. Although pH 5.9 was determined to be the optimum pH for the operation, subsequent experiments were still performed at the standard pH 7.0 because most of environmental samples have a pH value close to neutral pH and also because there is no signicant difference of the background-subtracted peak current at pH 7.0 and pH 5.9 (0.336 A vs. 0.355 A). The inset of Fig. 6 illustrates the differential pulse voltammetric response of the pTTP-modied electrode to successive addition of 50 ppb 2,4-DNT aliquots under optimal detection conditions, along with the voltammogram in buffer solution (background). The addition of 2,4-DNT results in well-dened reduction peaks and the peak currents are directly proportional to the analyte concentration. The assay is sensitive. Even a concentration of 50 ppb 2,4-DNT causes a signicant response without the need for any sample pre-concentration. The peak current of peak I is, after background-

3.5. Detection of other explosives on the pTTP-modied GC electrode The pTTP-modied GC electrode was also evaluated against other explosives under the standard conditions. Fig. 7ad show the dependence of the response to increasing concentrations of TNT, Tetryl, RDX, and nitromethane (the reduction peak I at 0.56, 0.45, 0.83 and 0.8 V were plotted, respectively). The insets of Fig. 7 present the DPV responses. The pTTP-modied GC electrode displays a wide dynamic range with good sensitivity for the nitroaromatic compounds TNT and Tetryl. The LOD was 8 ppb of TNT and 9 ppb of Tetryl, respectively. In addition, the pTTP lm also displayed good sensitivity for the alkylnitro compounds RDX and nitromethane, with the LOD of 96 and 43 ppb, respectively. These values are comparable to, or better than, the values for other reported explosives sensors [2,5,6,19,20,26,4547]. There is no signicant response for the investigated analytes on the control electrodes (bare GC, TTP-modied, polythiophene-modied; data not shown). The LODs for nitromethane and RDX are one order of magnitude higher than those for 2,4-DNT, TNT, and Tetryl. The better detection limits for the nitroaromatic compounds may be attributed to the fact that the nitroaryls are generally easily reduced than nitroalkanes. Further, the afnity of the aromatic porphyrins for nitroaromatic compounds is expected to be higher than for nitroalkanes. The pTTP-modied electrodes are stable. After the sensing experiments, the pTTP electrodes were rinsed with

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Fig. 7. Calibration plots for (a) TNT, (b) Tetryl, (c) RDX, and (d) nitromethane on the pTTP-modied GC electrode. The current responses for the reduction peak I are the values after background-subtraction. The insets show the original DPV data.

water and used for numerous additional measurements without any apparent loss in performance. 4. Conclusions In summary, conducting pTTP lms made by electropolymerization of the thienyl-derivatized porphyrin TTP onto GC electrodes possess excellent mechanical and electrical properties. Most significantly, the pTTP-modied GC electrodes can signicantly enhance the electrochemical reduction of the common explosives 2,4-DNT, TNT, Tetryl, RDX, and nitromethane in 0.01 M pH 7.0 phosphate buffer solutions. We attribute this to the afnity of the porphyrin in the polymer backbone for the analytes and its electrocatalytic properties. The modied electrode has a good response, dynamic range, and high sensitivity without the need for pre-concentration steps or using anodic stripping techniques. These features, combined with the ease of their preparation, make the novel conducting pTTP lm an attractive electrode material for the detection of explosives in aqueous solutions. Acknowledgments We greatly appreciate the funding from NSF and Science and Technology Directorate of the U.S. Department of Homeland Security. We thank Joshua Akhigbe for the preparation of TTP. Points of view in this document are those of the author(s) and do not necessarily represent the ofcial position of the funding agencies. References
[1] J. Wang, Electroanalysis 19 (2007) 415423. [2] J. Wang, R.K. Bhada, J.M. Lu, D. MacDonald, Anal. Chim. Acta 361 (1998) 8591. [3] K.C. Honeychurch, J.P. Hart, P.R.J. Pritchard, S.J. Hawkins, N.M. Ratcliffe, Biosens. Bioelectron. 19 (2003) 305312. [4] J. Yinon, Trac-Trends Anal. Chem. 21 (2002) 292301. [5] X.J. Fu, R.F. Benson, J. Wang, D. Fries, Sens. Actuator B 106 (2005) 296301.

[6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] [38]

J. Wang, S. Thongngamdee, Anal. Chim. Acta 485 (2003) 139144. U. EPA, EPA Method 8330, Washington, DC, 1995. T.L. Pittman, B. Thomson, W.J. Miao, Anal. Chim. Acta 632 (2009) 197202. I.U. Mohammadzai, T. Ashiuchi, S. Tsukahara, Y. Okamoto, T. Fujiwara, J. Chin. Chem. Soc. -Taip. 52 (2005) 10371042. E. Ercag, A. Uzer, R. Apak, Talanta 78 (2009) 772780. A. Uezer, E. Ercag, R. Apak, Anal. Chim. Acta 612 (2008) 5364. P.T. Charles, P.R. Gauger, C.H. Patterson, A.W. Kusterbeck, Environ. Sci. Technol. 34 (2000) 46414650. P.T. Charles, A.W. Kusterbeck, Biosens. Bioelectron. 14 (1999) 387396. P.T. Charles, J.G. Rangasammy, G.P. Anderson, T.C. Romanoski, A.W. Kusterbeck, Anal. Chim. Acta 525 (2004) 199204. E.R. Goldman, M.P. Pazirandeh, P.T. Charles, E.D. Balighian, G.P. Anderson, Anal. Chim. Acta 457 (2002) 1319. T.M. Green, P.T. Charles, G.P. Anderson, Anal. Biochem. 310 (2002) 3641. C.J. McHugh, R. Keir, D. Graham, W.E. Smith, Chem. Commun. (2002) 580581. J. Wang, S.B. Hocevar, B. Ogorevc, Electrochem. Commun. 6 (2004) 176179. R.G. Bozic, A.C. West, R. Levicky, Sens. Actuator B 133 (2008) 509515. J. de Sanoit, E. Vanhove, P. Mailley, P. Bergonzo, Electrochim. Acta 54 (2009) 56885693. D.L. Lu, A. Cagan, R.A.A. Munoz, T. Tangkuaram, J. Wang, Analyst 131 (2006) 12791281. J. Wang, M. Pumera, Anal. Chem. 74 (2002) 59195923. J. Wang, M. Pumera, G.E. Collins, A. Mulchandani, Anal. Chem. 74 (2002) 61216125. A. Hilmi, J.H.T. Luong, A.L. Nguyen, J. Chromatogr. A 844 (1999) 97110. S. Hrapovic, E. Majid, Y. Liu, K. Male, J.H.T. Luong, Anal. Chem. 78 (2006) 55045512. I. Grigoriants, B. Markovsky, R. Persky, I. Perelshtein, A. Gedanken, D. Aurbach, B. Filanovsky, T. Bourenko, I. Felner, Electrochim. Acta 54 (2008) 690697. S. Trevin, F. Bedioui, J. Devynck, J. Electroanal. Chem. 408 (1996) 261265. M. Pontie, H. Lecture, F. Bedioui, Sens. Actuator B 56 (1999) 15. F. Bedioui, S. Trevin, J. Devynck, F. Lantoine, A. Brunet, M.A. Devynck, Biosens. Bioelectron. 12 (1997) 205212. A. Ciszewski, G. Milczarek, J. Electroanal. Chem. 413 (1996) 137142. M.S. Ureta-Zanartu, C. Berrios, J. Pavez, J. Zagal, C. Gutierrez, J.F. Marco, J. Electroanal. Chem. 553 (2003) 147156. S.Y. Tao, G.T. Li, H.S. Zhu, J. Mater. Chem. 16 (2006) 45214528. B. Johnson-White, M. Zeinali, K.M. Shaffer, C.H. Patterson, P.T. Charles, M.A. Markowitz, Biosens. Bioelectron. 22 (2007) 11541162. S.Y. Tao, G.T. Li, Colloid Polym. Sci. 285 (2007) 721728. S.Y. Tao, G.T. Li, J.X. Yin, J. Mater. Chem. 17 (2007) 27302736. C. Bruckner, P.C.D. Foss, J.O. Sullivan, R. Pelto, M. Zeller, R.R. Birge, G. Crundwell, Phys. Chem. Chem. Phys. 8 (2006) 24022412. P. Bhyrappa, P. Bhavana, Chem. Phys. Lett. 349 (2001) 399404. M. Schaferling, P. Bauerle, J. Mater. Chem. 14 (2004) 11321141.

W. Chen et al. / Sensors and Actuators B 147 (2010) 191197 [39] [40] [41] [42] [43] [44] [45] [46] [47] M. Prochazka, N. Hajdukova, J. Stepanek, Biopolymers 82 (2006) 390393. Z.P. Zhang, F. Wang, F.E. Chen, G.Q. Shi, Mater. Lett. 60 (2006) 10391042. W. Chen, C.M. Li, P. Chen, C.Q. Sun, Electrochim. Acta 52 (2007) 28452849. A.K. Wanekaya, Y. Lei, E. Bekyarova, W. Chen, R. Haddon, A. Mulchandani, N.V. Myung, Electroanalysis 18 (2006) 10471054. H. Maruyama, H. Segawa, S. Sotoda, T. Sato, N. Kosai, S. Sagisaka, T. Shimidzu, K. Tanaka, Synth. Met. 96 (1998) 141149. T. Hasobe, S. Fukuzumi, P.V. Kamat, J. Am. Chem. Soc. 127 (2005) 1188411885. J.C. Chen, J.L. Shih, C.H. Liu, M.Y. Kuo, J.M. Zen, Anal. Chem. 78 (2006) 37523757. N.P. Saravanan, S. Venugopalan, N. Senthilkumar, P. Santhosh, B. Kavita, H.G. Prabu, Talanta 69 (2006) 656662. S. Trammell, F. Velez, P. Charles, A. Kusterbeck, Anal. Lett. 41 (2008) 26342645.

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Ying Wang is a graduate student at UConn, Department of Chemical, Materials and Biomolecular Engineering. She earned a Master degree in 2007 in Chemical and Biomolecular Engineering at Xiamen University, China. Her PhD research concentrates on the development of electrical and electrochemical sensors for explosive compounds. Changming Li is a professor of Bioengineering at Nanyang Technological University, Singapore. He received his PhD in Analytical Chemistry from Wuhan University, China, in 1987. His research is focused on engineering applications of bio- and nanotechnology, including microuidics, biosensors, fuel cells, and biomaterials. Christian Brckner is an associate professor of Chemistry at UConn. He received in 1996 his PhD in Organic Chemistry from the University of British Columbia, Canada. His research interests lie in synthetic porphyrin chemistry and the application of porphyrinoids as functional dyes in chemosensing, photodynamic cancer therapy, or as uorescent markers. Yu Lei is an assistant professor of Chemical, Materials and Biological Engineering at UConn. Dr. Lei obtained his PhD degree in 2004 at the University of California-Riverside in Chemical and Environmental Engineering. His current research combines biotechnology, nanotechnology, and sensing technology, especially as applied to the development of gas sensors, electrochemical sensors, and biosensors.

Biographies
Wei Chen is a postdoctoral fellow in the Department of Chemical, Materials and Biomolecular Engineering, University of Connecticut (UConn). He earned his PhD degree in 2008 in Bioengineering at Nanyang Technological University, Singapore. His research interests are centered on the electrochemical detection of biomarkers and explosives.