Sensors and Actuators B 137 (2009) 313319

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Sensors and Actuators B: Chemical

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A new stable Fe(CN)6 -immobilized poly(butyl viologen)-modied electrode for dopamine determination
Chih-Yu Hsu a , V.S. Vasantha a , Po-Yen Chen a , Kuo-Chuan Ho a,b,
a b

3/4

Department of Chemical Engineering; National Taiwan University, Taipei 10617, Taiwan Institute of Polymer Science and Engineering, National Taiwan University, Taipei 10617, Taiwan

a r t i c l e

i n f o

a b s t r a c t
A new kind of highly stable Fe(CN)6
3/4

Article history: Received 13 September 2008 Received in revised form 16 November 2008 Accepted 17 November 2008 Available online 24 November 2008 Keywords: Dopamine Electrocatalysis Ferrocyanide Mediated oxidation Poly(butyl viologen)

/poly(butyl viologen) (PBV) thin lm, without any sealing layer, as

4

a modied electrode for dopamine oxidation was proposed. In this work, Fe(CN)6 were entrapped within the PBV lm to form a charge transfer complex. The electrochemical and electrocatalytic properties were studied using cyclic voltammetry (CV) and amperometric techniques, in conjunction with a rotating-disk 3/4 electrode. The results show a highly stable and symmetric redox behavior for the Fe(CN)6 couple with peakpeak separation of 3 mV at a scan rate of 5 mV/s. The electron transfer rate constant for the 3/4 3/4 Fe(CN)6 couple within the lm, the catalytic rate constant between dopamine and Fe(CN)6 , and the MichaelisMenton constants are investigated. Moreover, the result shows an excellent mediation for dopamine oxidation. 2008 Elsevier B.V. All rights reserved.

1. Introduction Dopamine is a neuro-hormone released by hypothalamus. Exocytotoxic malfunction is involved in several neurodegenerative disorders such as Parkinsons and Alzheimers diseases, where the dopaminergic activity is lowered, as well as in schizophrenia where the activity of the dopaminergic neurons is increased due to abnormalities in their regulation [1,2]. The development of anorexia nervosa [3] and bulimia nervosa [4] has also been associated with malfunctioning dopaminergic activities. Hence, the development of electrochemical sensors for the determination of neurotransmitters has received great attention in the past [5,6]. The polymer-modied electrodes have been widely used as biosensors for their good stability, attractive catalytic ability, and broad potential window [710]. In our case, poly(butyl viologen), which belongs to ionic polymer type, is prepared by the electrochemical reductive polymerization method. Generally, viologen derivatives were used as effective reducing agents for dioxygen [11,12]. In addition, electrodes modied with the viologen reagents have been shown to be useful in hydrogen evolution catalysis [13,14], redox reactions of

biological molecules [15,16], binding of redox reactive metal complexes [17], and electrochromism [18]. In this study, poly(butyl viologen) (PBV) was prepared by the electrochemical reductive polymerization method, and the ferrocyanide ions were incorporated within PBV lm and used as a mediator for dopamine oxidation. According to the earlier reports, 3/4 Fe(CN)6 (we use this composite term to represent the redox
couple of Fe(CN)3 and Fe(CN)4 6 6 ) immobilized electrodes have been used as biosensors for detecting many bio-molecules [19]. So far only a few articles have been reported about dopamine 3/4 oxidation on Fe(CN)6 immobilized modied electrode [20,21]. In one of these cases also, the authors mentioned about leach3/4 from their modied electrode. To the best of ing of Fe(CN)6 3/4

our knowledge, the Fe(CN)6 /PBV-polymer modied electrode has not been reported earlier for the biosensor applications. Moreover, the stability of mediator, demonstrated in this study, is much 3/4 higher than that of Fe(CN)6 mediated biosensors reported earlier. In the present work, we focused on a detailed study about 3/4 electrochemical properties of Fe(CN)6 /PBV-polymer lm and its catalytic activity towards dopamine. 2. Experimental 2.1. Chemicals Dopamine used in our work was purchased from Sigma. KH2 PO4 , and KH2 PO4 were purchased from Aldrich and K4 Fe(CN)6 was

Presented at the 12th International Meeting on Chemical Sensors (IMCS-12), Columbus, Ohio, USA, July 1316, 2008. Corresponding author at: Department of Chemical Engineering; National Taiwan University, 1, Sec. 4, Roosevelt Rd., Taipei 10617, Taiwan. Tel.: +886 2 23660739; fax: +886 2 23623040. E-mail address: kcho@ntu.edu.tw (K.-C. Ho). 0925-4005/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.snb.2008.11.014

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purchased from Fisher Scientic. They were all reagent grade and used as received. Bis(4-cyano-1-pyridino)butane dibromide (BVBr2 ) were synthesized by following the procedure given in the report [22]. All aqueous solutions were prepared with deionized water (DIW) of resistivity of ca. 18.2 M cm. Experiments were all done at room temperature. 2.2. Apparatus All the cyclic and amperometric voltammograms were recorded with a potentiostat (CHI, model 440). The three electrode cell assembly consisting of Ag/AgCl/satd KCl/reference electrode and a platinum (Pt) foil counter electrode was used. The working elec3/4 /PBV/Pt-polymer modied surface trode was either the Fe(CN)6 or bare Pt surface. The rotating-disk electrode (RDE) experiments were performed by an analytical rotator (Pine, model AFMSRX) with a Pt disk of 0.5 cm in diameter. The spectrochemistry of monomer and Fe(CN)4 6 was studied using UVvis spectrometer of Shimadzu model UV-1601PC. 2.3. Preparation of Fe(CN)6
3/4

Fig. 1. Consecutive UVvis spectra recorded for the charge transfer complex formation between butyl viologen and ferrocyanide ions at different concentrations.

/PBV/Pt-modied electrodes were also observed when butyl viologen monomer was mixed with Fe(CN)4 6 solution. 3.2. Stability and electrochemical properties of the 3/4 /PBV system Fe(CN)6 Fig. 2(A) shows the CV of Fe(CN)6 /PBV lm scanned between 0.0 V and 0.45 V in the phosphate buffer solution (pH 7.4). It exhib3/4 ited a redox couple resulted from the immobilized Fe(CN)6 redox couple within the PBV lm. The formal potential of the redox couple was estimated from the two different formulas such as [Epa + Epc ]/2 and Epa (Epa Epc ) [25] ( = 0.37, see below) and found to be 0.2315 V and 0.2341 V, respectively. In order to check the 3/4 stability of the Fe(CN)6 /PBV lm-coated electrode, the modied electrode was immersed in the phosphate buffer solution (pH 7.4) and 200 consecutive CVs were recorded. The results are given 4 as the inset in Fig. 2(A). The peak currents of the Fe(CN)3 6 /Fe(CN)6 redox couple did not change much over 200 consecutive cycles between 0.0 V and 0.5 V and remained almost constant upon further cyclings. In general, the decay in peak currents was always observed 3/4 during stabilization of the Fe(CN)6 immobilized polymer electrodes [2628]. Hence, sealing layer of tetraethyl orthosilicate solgel coating lm was used to improve the stability of Tosex3/4 Fe(CN)6 modied electrodes [29]. Takita et al. reported that
40% of the Fe(CN)3 6 was released out of the poly(glutamic acid) lm-coated electrodes during stabilization [30]. However, no such instability was observed for our system which was attributed to the formation of charge transfer complex between Fe(CN)4 6 and monomer as veried by the UVvis absorption spectra. The electrochemical properties of the above-modied electrode were also collected using cyclic voltammetric method at different scan rates in the phosphate buffer solution. The electrochemical 3/4 /PBV lm should be similar to those responses of the Fe(CN)6 with a surface-conned redox couple, because the peak currents were directly proportional to the scan rate (see Fig. 2(B)) as predicted for a diffusionless system. The formal potential (E ) was almost independent of the potential sweep rates below 300 mV/s suggesting facile charge transfer kinetics over this range of sweep rates. In addition, the ratio of anodic to cathodic peak currents remained constant up to 300 mV/s. The peak separation, Ep , was found to be 3 mV at a scan rate of 5 mV/s. However, the peak separation began to increase with the increase of the scan rate, indicating 3/4

The PBV thin-lms were potentiostatically electropolymerized from BVBr2 . An aqueous medium containing 20 mM BVBr2 , 10 mM KH2 PO4 , 90 mM K2 HPO4 , and 100 mM K4 Fe(CN)6 was used for the deposition of Fe(CN)4 6 /PBV lm at a constant potential (0.75 V vs. Ag/AgCl/satd KCl) until an expected charge capacity was reached and then stepping to 0 V for 180 s. The resulting modied electrode were rinsed with DIW and then stored in air. In the present study, we for the rst time report about the 4 electrochemical properties of Fe(CN)3 redox couple 6 /Fe(CN)6 immobilized on the PBV lm and its excellent mediated electrocatalytic oxidation towards dopamine. 3. Results and discussion 3.1. UVvis spectrophotometric analysis
When monomer and Fe(CN)4 6 were dissolved in DIW, a colorless and a light yellow solutions, respectively, were obtained. However, mixing both these solutions resulted in a deep purple solution. Moreover, no precipitation occurred when the monomer and Fe(CN)4 6 mixed solution was used for electropolymerization. This phenomenon can be understood by the formation of charge transfer complexes between monomer and Fe(CN)4 6 . In order to conrm this phenomenon, UVvis spectroscopic experiment was carried out during the addition of different concentrations of Fe(CN)4 6 with monomer solution. In Fig. 1, the curve denoted by solid line () is attributed to UVvis absorption of 20 mM monomer solution alone and no absorption band was observed. Similarly, UVvis absorption spectrum was recorded for 1.0 M Fe(CN)4 6 solution in the same experimental conditions (labeled as ( )) and it exhibited a sharp absorption band at = 410 nm. However, a new broad absorption band between 420 nm and 700 nm was noticed with = 530 nm for the solution containing both Fe(CN)4 6 and the monomer (20 mM). The absorption spectra of the mixture are distinctly different from those of either parent components and hence they must be due to charge complex formation of the two components. Nakahara and Wang [23] reported that the methyl viologen ion (CH2 NC5 H4 C5 H4 NCH3 )+2 is a good electron acceptor because of the stability of its free radical ion discovered by Michaelis [24]. In Michaelis experiment, the UVvis spectrum was recorded when methyl viologen cations were mixed with electron donor such as Fe(CN)4 6 ions and conrmed the formation of charge transfer complex [24]. In our system, similar color as well as spectral changes

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315

Fig. 2. (A) Cyclic voltammograms of the Fe(CN)6 of the Fe(CN)6

3/4

3/4

/PBV lm in phosphate buffer solution (pH 7.4) at different scan rates. The inset is the consecutive cyclic voltammograms

/PBV lm. (B) The corresponding peak currents vs. scan rate up to 300 mV. (C) A plot of Ep E vs. log (scan rate).

the limitation arising from the charge transfer kinetics. From the CV 3/4 curve at 5 mV/s, the surface coverage of Fe(CN)6 redox couple is calculated from the following equation [31], = Qa nFAe (1)

is the scan rate (V/s), and where ip is the peak current (A), other symbols have their usual meanings. The value calculated is 2.14 108 mol/cm2 which is close to the value obtained from Qa . 3/4 This value is comparable with that of the Fe(CN)6 /polypyrrole modied electrode [35] and two orders of magnitude larger than 3/4 that of Fe(CN)6 dopped Tosex-modied electrode [29]. The heterogeneous rate constant, ks , of Fe(CN)6 species conned on PBV lm was calculated from the cyclic voltammograms obtained at different scan rates according to the procedure suggested by Laviron [36], i.e. n Ep > 200 mV/n. In our case, at a scan rate above 1000 mV/s, the Ep was found to be exceed 200 mV for one electron transfer. Fig. 2(C) shows the plot of Ep E vs. log for the scan rate above 1000 mV/s. It was found that Ep E varies linearly with log . Under this conditions, (charge transfer coefcient) and ks were calculated from Eq. (3),
RT nF (1 )nF Ep 2.3RT
3/4

where is the surface coverage (mol/cm2 ), Qa is the charge under the anodic peak which was obtained by integrating the area under the anodic peak (C), n is the number of electrons consumed (n = 1), F is the Faradays constant, and Ae is the geometric area of the electrode (cm2 ). The obtained values of Qa , and C (the concentration 8 mol/cm2 of the redox molecule, Fe(CN)4 6 ) are 57.04 C, 1.88 10 3 and 0.641 mol/dm , respectively. The apparent surface coverage was also calculated from the slope of the plot of peak current vs. scan rate (Fig. 2(B)) using this formula [3234], ip = n2 F 2 Ae 4RT (2)

log ks = log(1 ) + (1 ) log log

(3)

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Fig. 3. (A) Cyclic voltammograms of the Fe(CN)6

3/4

/PBV lm in phosphate buffer solution (pH 7.4) in the absence of dopamine (solid line) and in the presence of 1 mM
3/4

dopamine (dotted line). (B) Voltammograms of the Fe(CN)6 /PBV lm in phosphate buffer solution (pH 7.4) in the presence of different concentrations of dopamine (0.25 mM dopamine at each increment). The inset is a plot of current density vs. dopamine concentration.

where was calculated from slopes and using the formulas 2.3RT/nF (cathodic) or 2.3RT/(1 )nF (anodic), and being found to be 0.37, used was 1 V/s and its corresponding Ep (0.202 V) was used. Other symbols have their usual meanings. The value of the heterogeneous reaction rate constant, ks , is found to be 0.39 s1 . This value is comparable with that obtained for the 3/4 Fe(CN)6 /polypeptide composite electrode (0.25 s1 ) [37]. 3.3. Electrochemical oxidation of dopamine The mediated catalytic property of the above lm was tested for dopamine oxidation in the phosphate buffer solution at pH 7.4 and the corresponding cyclic voltammogram was given in Fig. 3. When the lm was placed into the buffer solution, a pair of redox 3/4 peaks attributing to the Fe(CN)6 redox couple was observed. When dopamine was added to the solution, the oxidation peak cur3/4 rent (at 0.220 V) of Fe(CN)6 ions immobilized on the PBV-lm modied electrode increased whereas the reduction peak current decreased in the reverse scan, as shown in Fig. 3(A). This behavior is typical and is expected for a mediated oxidation of dopamine by 3/4 the Fe(CN)6 mediator. But under the same condition, electro-

chemical signal was observed at 0.350 V for dopamine at the bare Pt surface (not shown in gures). The cyclic voltammograms were also obtained at various concentrations of dopamine in the conditions mentioned above (Fig. 3(B)). Upon the addition of dopamine up to 2 mM, a linear increase in the anodic peak current was observed in the forward scan and a decrease in the cathodic peak current was noticed in the reverse scan. However, the decrease in the cathodic peak current was not as appreciable as that found in the anodic side. The formation of dopaminequinone (oxidative state of dopamine) during the forward scan at higher concentration of dopamine became larger, thus the reduction current was overlapped with the Fe(CN)3 6 reduction in the reverse scan. From the viewpoint of sensor applications, the long-term stability, or reusability, as well as the selectivity of the electrode for dopamine sensing are important. When the electrode was stored in air then tested in a 1 mM dopamine solution, our preliminary at-rest stability data based on the oxidation peak current of cyclic voltammograms showed 10% decay over a period of 5 days storage. As for the selectivity, ascorbic acid and uric acid were normally chosen as the major interferences towards dopamine, since these three species undergo electrochemical oxidations almost at the same potential on the conventional electrode. To tackle this prob-

Fig. 4. (A) Amperometric it curves for dopamine oxidation in the concentration range of 20 M to 2 mM at different electrodes in phosphate buffer solution. (B) Calibration curves derived from (A) against dopamine oxidation for different electrodes.

C.-Y. Hsu et al. / Sensors and Actuators B 137 (2009) 313319 Table 1 The kinetic parameters obtained for electrode A and B. Electrodes A( = 1.55 10
8

317

Methods mol/cm )
2

KM (mM) 5.82 5.52 5.75 5.70 0.12 4.38 4.34 4.38 4.37 0.02

iM (A) 1041 1002 1030 1024 15 758 752 758 756 3

kc (s1 ) 1.78 1.71 1.76 1.75 0.03 2.25 2.23 2.25 2.24 0.01

R 0.9998 0.9956 0.9972 0.9999 0.9988 0.9994

LineweaverBurke EadieHoftsee Hanes Average LineweaverBurke EadieHoftsee Hanes Average

B(

= 8.9 109 mol/cm2 )

lem, Naon [38] was usually chosen as an ion-exchange resin to improve the selectivity in this system. The stability, or reusability, as well as the selectivity for the electrode coated with a Naon layer are under investigation. 3.4. Kinetic parameters for dopamine/Fe(CN)6
3/4

In this study, the chronoamperometric technique was used to 3/4 investigate the electro-catalytic function of Fe(CN)6 within the PBV lm towards the electro-oxidation of dopamine. Fig. 4(A) shows the amperometric curves for the electro-catalytic oxida3/4 tion of dopamine at the Fe(CN)6 /PBV modied electrodes (A, B and C) with different surface coverages of mediator, including 1.55 108 mol/cm2 (curve A) and 8.90 109 mol/cm2 (curve B) and zero surface coverage on a bare Pt electrode as well (curve C). When the dopamine was added, the catalytic current increased up to 1.25 mM and slowly reached the saturation in the concentration range of 1.255 mM. This asymptotic behavior suggests the existence of an electrochemical reaction with the formation of an intermediate complex between mediator and dopamine followed by its decomposition. In fact, such electrocatalytic behavior has been observed for dopamine [39] without invoking electrocatalytic modeling. Subsequently, electrocatalytic mechanism has been proposed for a similar compound of dopamine, ascorbic acid [26,40]. The electrocatalytic steps proposed in our study are quite similar to the MichaelisMenten (MM) mechanism, as shown below:
2[PBV2+ Fe(III) (CN)3 6 ] + DH2 kc k1 k1 {2[PBV2+ Fe(III) (CN)3 6 ] DH2 }

+ 2[PBV2+ Fe(II) (CN)4 6 ] + DQ + 2H

(4)

2+ 2[PBV2+ Fe(II) (CN)4 Fe(III) (CN)3 6 ]2[PBV 6 ] + 2e

ks

(5)

(EH) and Hanes were used to evaluate the kinetic parameters, including KM , kc and iM from the slopes and intersects of linear plots of these equations, e.g. (iCAT )1 vs. (CDH2 )1 of LB plot, iCAT vs. iCAT /CDH2 of EH plot and (CDH2 /iCAT ) vs. CDH2 of Hanes plot. The corresponding kinetic parameters are listed in Table 1. From the data, it is understood that KM and iM increased directly proportional to the surface coverage as observed by Vaillancourt et al. [43]. From Fig. 4(A), it is understood that the time it takes to reach the maximum catalytic current is ca. 4 s (as shown in the inset) and the signal remains constant after each addition even at high concentrations, whereas, at the bare Pt electrode the current is not steady at higher concentrations. This suggests that the occurrence of electrode fouling at the bare electrode is due to the adsorption of oxidized species of dopamine. By plotting the current density vs. concentration (Fig. 4(B)), the sensitivities of electrodes A, B and C were calculated to be 0.800 mA/mM cm2 , 0.732 mA/mM cm2 and 0.610 mA/mM cm2 , respectively. Besides, the theoretical sensitivities for electrodes A and B can be calculated from the ratio of iM /KM , which are 0.917 mA/mM cm2 and 0.887 mA/mM cm2 , respectively. The oxidation current of dopamine increases linearly with the concentration in the range of 20 M to 1.25 mM for electrodes A and B. This linear range is found to be higher than recently reported values [4446]. Moreover, the detection limit (with a signal to noise ratio, S/N = 3) for electrodes A and B are around 2.46 and 2.34 M, respectively, and these values are slightly lower than that of the reported values [4446]. Presumably, it is originated from the redox cou3/4 ple of Fe(CN)6 , which is present within the modied electrode and causes the perturbation in the background current during the detection of dopamine. The rate constant of the electro-catalytic process between 3/4 dopamine and the immobilized Fe(CN)6 for electrode A was also obtained by using a rotating disk electrode (RDE) performing at different rotating rates (Fig. 5). The KouteckyLevich equation, which relates the current to the rotating rate, can be written as 1 1 = IL (n1 FAe kapp cDH2 + 1 (0.62n1 FAe D2/3
1/6 1/2 c DH2 )

where DH2 is the dopamine, DQ is the dopaminequinone, KM = (kc + k1 )/k1 is the apparent MM constant (mol/cm3 ), kc is the complex decomposition rate constant (s1 ), ks is the heterogeneous rate constant (s1 ). The MM equation for the above mechanism is shown as Eq. (6) iCAT = n1 FAe kc cDH2 KM + cDH2 (6)

(9)

where iCAT is the catalytic current, n1 is the number of electrons involved in the overall catalytic reaction (n1 = 2), and all other symbols have their usual meanings. Eq. (6) can be re-written as iCAT = iM cDH2 KM + cDH2 (7)

where iM is the maximum catalytic current (A), which is given by iM = n1 FAe kc (8)

Based on the earlier reports [4042], several transformations of MM equation such as LineweaverBurke (LB), EadieHoftsee

where IL is the limiting current (A), kapp is the apparent electrocatalytic rate constant (M1 s1 ), D is the diffusion coefcient of dopamine (cm2 /s), is the kinematic viscosity (cm2 /s), and is the rotating rate (rad/s). It is noted that 1 rpm (revolutions per minute) equals 0.10471976 rad/s (radian per second). Since the catalytic current for the dopamine oxidation follows the KouteckyLevich equation, thus the process might be controlled by the surface reaction. From the intercept of 1/IL vs. 1/2 (inset of Fig. 5), kapp was calculated to be 7.58 102 (M1 s1 ). Thus, the rate constant of the mediator reacted with dopamine within the lm can be obtained. The kapp can be considered as the overall rate constant of the reaction in Eqs. (4) and (5). To the best of our knowledge, no related literature reported the kinetic parameters regarding the reaction 3/4 between dopamine and Fe(CN)6 , including the MM constant and the electro-catalytic constant.

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Fig. 5. The LSV curves for the Fe(CN)6 /PBV lm (at 100 mC/cm2 PBV) obtained at a RDE in the presence of 7 mM dopamine at different rotating rates. Supporting electrolyte: 0.01 M phosphate buffer (pH 7.4). The inset shows a plot of i1 vs. 1/2 (KoutechyLevich plot).

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4. Conclusions The Fe(CN)6 mediator was strongly immobilized within the PBV lm and its electrochemical properties were studied. It is found 3/4 that the stability and the reversibility of Fe(CN)6 mediator within the PBV lm in phosphate buffer solution are reasonably good, thus can be applied to the eld of electrocatalysis. The good stability observed in our study is resulted from the formation of charge transfer complex by Fe(CN)4 6 and butyl viologen monomer. The kinetic parameters such as the formal potential (E ), the transfer coefcient () and the apparent charge transfer rate constant (ks ) were found to be 0.232 V, 0.37 and 0.39 s1 , respectively. 3/4 /PBV lm modied electrode showed an effecThis Fe(CN)6 tive mediated oxidation towards dopamine. The electrochemical 3/4 /PBV lm towards dopamine oxidabehavior of the Fe(CN)6 tion was studied by cyclic voltammetric, chronoamperommetric, and rotating disk electrode techniques. The catalytic oxidation of 3/4 dopamine on the Fe(CN)6 /PBV lm modied electrode followed the MM mechanism. For electrode A which has better performance in dopamine oxidation, the obtained apparent MM constant (KM ), the maximum catalytic current (iM ), and the complex decomposition rate constant (kc ) were 5.70 mM, 1024 A, and 1.75 s1 , respectively. From the RDE experiment, the apparent electro3/4 was catalytic rate constant between dopamine and Fe(CN)6 2 1 1 found to be 7.58 10 M s . The catalytic current of dopamine 3/4 at the Fe(CN)6 /PBV lm was used to determine the dopamine concentration in aqueous solution at pH 7.4. The sensing electrode exhibited a linear sensitivity of 0.800 mA/mMcm2 up to 1.25 mM and a detection limit about 2.46 M. Acknowledgements This work was nancially supported by the National Science Council of Taiwan, the Republic of China, under grant number NSC 95-2221-E-002-353-MY2. References
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V.S. Vasantha received her B.S. degree in Department of Chemistry from Madurai Kamaraj University, India in 1985. She received her M.S. and Ph.D. degrees in Department of Industrial Chemistry with specialization of electrochemistry at the Alagappa University, India in 1988 and 1994, respectively. She was a post-doctoral fellow appointed by the Department of Chemical Engineering at National Taiwan University (2007). Her interested elds are electrochemistry, electrodeposition, chemically modied electrodes, and bio-sensors.

Po-Yen Chen received his B.S. and M.S. degrees in Department of Chemical Engineering from National Chung Hsing University, Taiwan in 2001 and 2003, respectively. He is now pursuing his Ph.D. degree in Department of Chemical Engineering, National Taiwan University. His interested elds include electrochemistry, chemically modied electrodes, and molecularly imprinted polymer sensors.

Kuo-Chuan Ho received his B.S. and M.S. degrees in Department of Chemical Engineering from National Cheng Kung University, Taiwan in 1978 and 1980, respectively. He received his Ph.D. in Chemical Engineering at the University of Rochester, USA in 1986. Currently he is a Professor jointly appointed by the Department of Chemical Engineering and Institute of Polymer Science and Engineering at National Taiwan University. His research interests mainly surround applications of chemically modied electrodes on sensing and electro-optical devices.

Biographies
Chih-Yu Hsu received his B.S. degree in Department of Chemical Engineering from National Taiwan University, Taiwan in 2005. Currently, he is a Ph.D. candidate in Department of Chemical Engineering at National Taiwan University. His research interests cover electrochemical analysis based on chemically modied electrodes and applications of electrochemistry to bio-sensing and electro-optical devices.