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Electrochimica Acta 52 (2007) 2181–2188

Electrocatalytic oxidation of deoxyguanosine on a glassy
carbon electrode modified with a ruthenium oxide
hexacyanoferrate film
Thiago R.L.C. Paix˜ao, Mauro Bertotti ∗
Instituto de Qu´ımica, Universidade de S˜ao Paulo, S˜ao Paulo 05508-900, SP, Brazil
Received 22 May 2006; received in revised form 18 August 2006; accepted 19 August 2006
Available online 20 September 2006

The electrocatalytic oxidation of deoxyguanosine on a ruthenium hexacyanoferrate (RuOHCF) glassy carbon (GC) modified electrode was
investigated in acid medium by using rotating disc electrode (RDE) voltammetry. Chronoamperometric experiments allowed information on
the charge transport rate through the RuOHCF film and at a very short time window a diffusion-like behavior was observed with a Dct value of
2.7 × 10−11 cm2 s−1 for a film with Γ = 4.47 × 10−9 mol cm−2 . The influence of systematic variation of rotation rate, film thickness and the electrode
potential indicates that the rate of cross-chemical reaction between Ru(IV) centers immobilized into the film and deoxyguanosine controls the
overall electrodic process and the value of the rate constant was found to be 3.2 × 106 mol−1 L1 s−1 . The relatively high rate constant of the crossreaction, the facile penetration of the substrate through the film and the fast transport of electrons suggest that the electrocatalytic process occurs
throughout the film layer.
© 2006 Elsevier Ltd. All rights reserved.
Keywords: Modified electrodes; Rotating disc electrode; Deoxyguanosine; Ruthenium hexacyanoferrate film

1. Introduction
The electrochemical behavior of nucleobases or nucleobase
moieties (nucleosides and nucleotides) at solid electrodes was
firstly investigated at pyrolytic electrodes (PGE) [1–5]. Other
studies were reported by using highly oriented pyrolytic graphite
[6,7], carbon paste [7], glassy carbon (GC) [8,9], carbon fiber
[8], carbon nanotubes [9,10], boron-doped diamond [11], gold
[12,13] and indium tin oxide electrodes [14]. The great interest in this subject is certainly justified by the development of
electrochemical sensors for DNA.
The anodic oxidation of DNA gives rise to two well-defined
peaks at positive potentials. These two peaks are related to the
oxidation of both guanine and adenine moieties (or more properly, deoxyguanosine and deoxyadenosine when the free bases
are added as sugar constituents in the DNA). The structural and
stabilizing effects resulting from the interaction of these free

Corresponding author. Tel.: +55 11 3091 3837; fax: +55 11 3815 5579.
E-mail address: (M. Bertotti).

0013-4686/$ – see front matter © 2006 Elsevier Ltd. All rights reserved.

bases with the DNA molecule causes the anodic processes to be
shifted (0.2–0.3 V) to more positive potentials [15].
Literature [16,17] reports that deoxyguanosine [18]
(Scheme 1) can react with polyunsaturated fatty acids (PUFAs)
in the lipid peroxidation under oxidative conditions. This reaction may cause damages in the DNA structure, resulting in a
disruption of the double helix structure and allowing the guanine sites to be more accessible [19].
Electrochemical sensors provides an attractive, simple and
inexpensive approach to monitor DNA damages as they minimize the need for labeling the target nucleic acids and may
provide information with spatial resolution [20–26]. Notwithstanding, the oxidation peaks in native DNA are smaller than
in the denaturized species because the nucleobases are hidden
inside the helix and the rigidity of the structure keeps them
far from the electrode surface [1]. For this reason, methods
involving the modification of electrode surface with ruthenium
complexes, that exhibit electrocatalysis properties to the guanine
oxidation, have been exploited to enhance the sensitivity of analytical determinations [27–37]. These studies demonstrate the
usefulness of the immobilization of polymeric or non-polymeric

Measurements were done on a glassy carbon plate of 1 cm2 geometric surface area (Alfa Aesar. Authors [39. Solutions with this composition were used as supporting electrolyte throughout this work.5 mol L−1 NaNO3 + 0.3 V at 100 mV s−1 in supporting electrolyte (0. comparative experiments were also carried out with Prussian blue films (FeHCF) containing no ruthenium centers. Electrodes and instrumentation An Autolab PGSTAT 30 (Eco Chemie) bipotentiostat with data acquisition software made available by the manufacturer (GPES 4. Accordingly.8 version) was used for electrochemical measurements. In order to improve the understanding of this system and to contribute to the design of a sensor for DNA damages in a logical and rational manner. The modification of the electrode surface with this film was accomplished by cycling the potential between −0. Massachusetts. Thorp and co-workers proposed a mechanism to describe the electrocatalytic mediation of guanine oxidation by Ru(bpy)3+ [31–34]. the focus was concentrated on the kinetics of the electrocatalytic oxidation of deoxyguanosine at RuOHCF modified electrodes. Voltammetry with a glassy carbon rotating disc electrode (RDE) was carried out using an analytical rotator (AFMSRX. Germany) as described elsewhere [42]. In order to evaluate the ability of the substrate (deoxyguanosine) to penetrate through the modifier film. we present in this work some results on the electrocatalytic properties of a glassy carbon electrode modified with an electrodeposited film of ruthenium(III) hexacyanoferrate (RuOHCF) towards the electrocatalysed oxidation of deoxyguanosine. Morphological examination of electrodes covered with RuOHCF and Prussian blue (FeHCF) layers was performed by analysis of micrographs obtained with a Cambridge microscope (LEO Stereoscan 440). The amount of immobilized material at the electrode surface after potentiodynamic experiments was controlled by the number of potential cycles and the surface excess (Γ ) was determined from the charge under the voltammetric peak for the Ru(II/III) (or Fe(II/III) for the Prussian blue film) redox process. After film formation. 2. Chemical and materials All solid reagents were of analytical grade and were used without further purification. equipped with an Oxford Link ISIS energy dispersive spectrometer (EDS) that allows the elemental composition of materials imaged in a scanning electron microscope (SEM). methionine.2 and 1. In particular.38]. ascorbic acid.05 mol L−1 HCl) aqueous solution containing 1 mmol L−1 K3 Fe(CN)6 and 1 mmol L−1 RuCl3 .40] demonstrated that these films exhibit some electrocatalytic properties related to the oxidation of cysteine.R.2 × 10−11 + 1. A homemade Ag/AgCl (saturated KCl) and a platinum wire were used as reference and counter electrodes. Bertotti / Electrochimica Acta 52 (2007) 2181–2188 Scheme 1. measurements being performed in a vertical computer-controlled DRE-EL02 Ellipsometer (Ratzeburg. where Γ is the surface excess (mol cm−2 ) and L is the thickness of the film layer (cm) measured by ellipsometry. Barnstead). (2)) enhancing the oxidation current: Ru(bpy)3 2+  Ru(bpy)3 3+ +e − Ru(bpy)3 3+ + guanine → Ru(bpy)3 2+ + (guanine)ox (1) (2) Recent works [39–41] have shown the preparation of a new hexacyanoferrate film with ruthenium as redox center.5 mol L−1 NaNO3 + 0. Experimental 2.05 mol L−1 HCl and performing repetitive potentiodynamic cycling between the pre-set potential limits. Alfa Aesar. The electrochemical deposition of the RuOHCF film was accomplished by potentiodynamic cycling between pre-set potential limits of −0. the underlying physical processes have been elucidated. The concentration of the redox active centers in the RuOHCF film was calculated by using the following formula: bo (mol cm−3 ) = Γ /L. Germany). 2. Massachusetts. respectively. films containing ruthenium complexes to investigate damages in the DNA structure by carcinogenic compounds [27–30.0 V at 100 mV s−1 in a solution containing 2. A linear relationship between potentiodynamic cycles (n) and surface excess was established as Γ (mol cm−2 ) = −8.2. Paix˜ao. rinsed with water and sonicated for 5 min in distilled water.1. 2. the electrode was rinsed with deionized water. The formation of the RuOHCF film on the glassy carbon disc surface was verified by immersing the modified electrode in a supporting electrolyte solution containing 0.5 mmol L−1 FeCl3 + 2. Potassium ferricyanide and sodium nitrate were obtained from Merck (Darmstadt.35 × 10−10 n (n in the range 5–60 cycles) for the RuOHCF film. The thickness of the RuOHCF films electrodeposited onto the GC electrode was determined by ellipsometry. (1)) reacts with the substrate inside the film layer (Eq. ruthenium(III) chloride was obtained from Alfa Aesar (Massachusetts. The working electrode was a glassy carbon electrode (d = 3 mm). EUA) and guanine and deoxyguanosine were obtained from Sigma–Aldrich (Steihheim.2182 T.L.5 mmol L−1 K3 Fe(CN)6 . According to these authors. In almost all cases the solutions were prepared by dissolving the reagents in deionized water processed through a water purification system (Nanopure Infinity. Germany). Modification of the electrode surface The surface of the GC electrode was polished with alumina suspension (1 ␮m. sulfur oxoanions and alcohol. Pine Instrument Company) connected to the potentiostat.C. the electrogenerated mediator (Ru(bpy)3+ ) (Eq.5 and 1. EUA). cystine. M.3. EUA) on a microcloth polishing pad. .

The increased stability of the film layer has been attributed to the incorporation of ruthenium atoms that restrain the dissolution owing to the already reported formation of bridging oxo bonds 2183 (5) Na2 RuIII O[FeIII (CN)6 ]  NaRuIV O[FeIII (CN)6 ] + Na+ + e− (6) Charge transfer through the electroactive RuOHCF film probably occurs via an electron hopping process with simultaneous uptake of counter ions to provide charge balance. 2. voltammograms such as those shown in Fig.-) and FeHCF (Γ = 2. EDS spectra of RuOHCF (Γ = 7. Scan rate: 100 mV s−1 . four pairs of cathodic and anodic peaks are observed at around 0 V (a). 2 are obtained. By transferring the prepared RuOHCF modified electrode to the supporting electrolyte solution.R. Data were obtained at different film thickness values and the results are shown in Fig. as expected for a surface confined process. M. The linear plots with zero intercept demonstrate that charge transport is fast at relatively short .44]..C. as the acidity was increased. Bertotti / Electrochimica Acta 52 (2007) 2181–2188 Fig. current is a linear function of t−1/2 . Rb+ and Cs+ .e. Na4 RuII O[FeII (CN)6 ]  Na3 RuIII O[FeII (CN)6 ] + Na+ + e− Peak b : Peak c : (4) Na3 RuIII O[FeII (CN)6 ]  Na2 RuIII O[FeIII (CN)6 ] + Na+ + e− Peak d : (3) NaRuIII [FeII (CN)6 ]  RuIII [FeIII (CN)6 ] + Na+ + e− 3. Paix˜ao.9 V (c) are symmetrical.1. hence experiments in this work were performed with solution pH values around 2. A steady-state voltammetric profile is observed after a few potential cycles and the response of the modified electrode is maintained unchanged for at least 3 h during which the potentiodynamic experiment was performed continuously. confirming the existence of ruthenium oxide in the composite film. 0. Micrographs of a glassy carbon surface before (A) and after (B) electrodeposition of a RuOHCF film. 3. Electrochemical behavior of the RuOHCF modified electrode Repetitive potential cycles in a Ru(III) + Fe(CN)6 3− solution yields to the in situ deposition of an insoluble material onto the GC electrode surface. 1. Additionally. current rises from zero to a peak value and then falls again to almost zero.5–3. Na+ . at less acidic conditions a film loss has been reported by Budnikov and co-workers [39].21 × 10−8 mol cm−2 ) (—) films. the peak potential separation is close to zero in both cases and that the current peak is proportional to the scan rate. These results indicate that the charge propagation is fast and relatively unimpeded.5 mol L−1 NaNO3 + 0. 3. Results and discussion between Ru and Fe atoms [43. By comparing the EDS spectra it is clearly seen that the amount of oxygen in the RuOHCF film is much higher.80 × 10−9 mol cm−2 . A similar conclusion is evidenced by noticing that electrochemical processes at 0 V (a) and 0. The four pairs of peaks have been attributed in the literature [40] to the following electrodic processes in supporting electrolyte containing Na+ cations: Peak a : Fig. By looking at Fig.L. Peak potential separation for the first peak (a) was close to zero by varying the scan rate in the range 5–110 mV s−1 and for a modified electrode with Γ = 7. were observed for all four redox couples (in the pH range 0. On the other hand. The high conductivity of the RuOHCF-coated film was also confirmed by chronoamperometric experiments carried out in supporting electrolyte solution. as well as EDS spectra obtained with FeHCF and RuOHCF films. [40] studied the influence of the supporting electrolyte composition on the voltammetric profile of RuOHCF films and demonstrated that only the first peak (at less positive potentials. K+ .0). the influence of pH was more pronounced and positive potential shifts. Chen et al. as reported in previous studies [39–41] and the continuous current increase demonstrates the growth of the film layer. At relatively short times the distance of charge transport (proportional to (Dt)1/2 ) is lower than the film thickness and the semi-infinite condition prevails.1 V (d). hence chronoamperometric curves should follow the Cottrell equation.T.05 mol L−1 HCl)..80 × 10−9 mol cm−2 ) (. 0. peak a) is affected by cationic species such as Li+ . Micrographs of the glassy carbon plate before and after deposition of the RuOHCF film are shown in Fig. For the first pair of peaks (a).9 V (c) and 1. The evaluation of the rate of charge transport through the coat was firstly studied by cyclic voltammetry. These plots demonstrate the relationship between the diffusion layer thickness and the film thickness. 2.0.7 V (b). 1. Consecutive voltammograms recorded with the RuOHCF modified electrode in supporting electrolyte solution (0. i.

Potential step from 0.09 2. respectively (Table 1). From coatings prepared with 15. Plots of the limiting currents in the form of a Levich plot for coatings with different thicknesses are also shown in this Fig.5 mol L−1 NaNO3 + 0. Cyclic voltammograms recorded in supporting electrolyte solution before (. The fact that an attenuation of the cathodic peak at around 1.2184 T. indicating that a kinetic limitation controls the overall process. The slight decrease observed in Dct for thicker films is likely to be explained by difficulties in charge compensation by counter ions diffusion.05 mol L−1 HCl. 4. this being an Fig.80 × 10−9 mol cm−2 (c). Data were obtained with various rotation speeds and thicknesses of modifier to obtain information on the possible rate-determining step as well as on the location of the reaction zone. Fig. Two main points should be emphasized: i.81 4. for the film prepared with 15 potential cycles the time is 185 ms.9 × 10−11 cm2 s−1 .. Electrocatalytic oxidation of deoxyguanosine The electrocatalytic role of the RuOHCF modified electrode on the oxidation of deoxyguanosine is presented in Fig. M. Kouteck´y-Levich plots for different potentials (Fig. evidence that electrochemically generated Ru(IV) oxidizes the biomolecule. Bertotti / Electrochimica Acta 52 (2007) 2181–2188 Fig. On the other hand.81 × 10−9 mol cm−2 (a). 5(C). The catalytic efficiency of the RuOHCF modified electrode towards the oxidation of deoxyguanosine was estimated by comparing signals obtained with the modified and the bare electrode. IL is independent of the rate of rotation at relatively high ω values. which also shows the anodic process involving this substrate at a bare GC surface. 3.37 3. The dashed lines correspond to the linear regression of data collected in the short time region.81 × 10−9 mol cm−2 ). these data are strong evidence that there is no limitation arising from charge-transfer kinetics within the RuOHCF film.1 V is also an evidence of the electrocatalytic oxidation of deoxyguanosine at the RuOHCF modified electrode. 4.89 1/2 .2.73 2. It is instructive to observe that at the lowest rotation rate the limiting current driven by the modified electrode Table 1 1/2 Values of Dct bo and Dct for different Γ and L (measured by ellipsometry) values Γ × 109 /mol cm−2 Thickness × 106 /cm bo × 103 /mol cm−3 Dct bo × 109 /mol cm−2 s−1/2 Dct × 1011 /cm2 s−1 1.47 7. modified electrodes were used in rotating disc electrode voltammetric experiments. Dct values were found to vary in the range 2. Chronoamperometric current/time data for RuOHCF modified electrodes with different Γ values: 1. one can calculate the time taken to fully oxidize the Ru(III) centers incorporated into the film by using the expression [45]: t= L2 πDct (7) For instance. Notwithstanding.05 mol L−1 HCl.C.89 4. The electron transfer involving deoxyguanosine occurs at the potential where Ru(III) is oxidized.R. which reinforces the conclusions on the very high charge transport through the RuOHCF coating.80 3.7 × 10−11 to 1. 5A shows voltammograms recorded at different rotation speeds with a RuOHCF modified electrode (Γ = 10. at longer times the diffusion layer becomes as thick as the film layer and the transition to the thin-layer behavior is noticed by the deviation of the plots from linearity.458 0. 5B) along the voltammetric waves give parallel straight lines. Paix˜ao. In order to investigate in more details the electrocatalytic process.3 × 10−10 mol cm−2 ) in supporting electrolyte solution containing deoxyguanosine.-) and after (—) addition of deoxyguanosine (final concentration in solution = 1 mmol L−1 ) by using a bare glassy carbon electrode (A) and a RuOHCF (B) modified electrode (Γ = 1. Accordingly.72 1. a 9fold current enhancement being observed at these experimental conditions. 4.47 × 10−9 mol cm−2 (b) and 7. 30 and 60 potential cycles.L.95 5. Scan rate: 100 mV s−1 . which is an indication that the reaction is firstorder in deoxyguanosine [46].746 1. The quantitative basis for this assumption would take into account the layer thickness (L) and the corresponding Dct value shown in Table 1.69 2. time windows.5 mol L−1 NaNO3 + 0. Supporting electrolyte: 0.0 to 1.17 0. 3.2 V in a solution containing 0.99 7.

By noticing that current values are similar using the modified electrode and the bare GC electrode (Fig.T.e. The slope of the straight line was found to be 0. at these experimental conditions the influence of mass transport on the overall electrodic process is relevant.-) and after (—) addition of deoxyguanosine (final concentration in solution = 2 mmol L−1 ) by using a bare glassy carbon electrode (A) and a glassy carbon electrode coated with a Prussian blue film (B) (Γ = 2.05 mol L−1 HCl using a RuOHCF modified electrode (Γ = 1.48] theory.930.R.21 × 10−8 mol cm−2 ) than those typically used for RuOHCF modified electrodes. Considering the Albery and Hillman [47. in this specific case. 1600 rpm (d) and 2500 rpm (e). it may be concluded that the substrate diffuses freely through the Prussian blue layer which is. Fig. confirm the usefulness of using Eq. At any fixed rotation rate the limiting catalytic current increases with increasing the thickness of the coating. containing larger loadings approaches the one predicted by the Levich equation. The intercept values (ω−1/2 = 0) being inversely proportional to Γ .. 11.15 V (a). Levich plots (C) for RuOHCF modified electrodes with different Γ values: 9. Paix˜ao.21 × 10−8 mol cm−2 ).5 mol L−1 NaNO3 + 0. cs is the bulk concentration of substrate. Inset (B) shows Kouteck´y-Levich plots for current values measured at different potentials: 1. Scan rate: 100 mV s−1 . Cyclic voltammograms recorded in supporting electrolyte solution before (. Scan rate: 20 mV s−1 . i. For such an electrodic system the characteristic current for substrate diffusion may be determined by the Kouteck´y-Levich analysis by using the relationship: −1  (Ilim )−1 = (nFAkMEc ) s −1 + (0. This is usually done by evaluating the limiting current at an infinite rotation rate via a Kouteck´yLevich plot. 7A.20 V (c) and 1. M. no kinetic information being available. ii. ν is the kinematic viscosity.8 × 10−10 mol cm−2 (d). 400 rpm (b). .05 mol L−1 HCl. The solid line (e) corresponds to the linear regression of simulated data calculated using the Levich equation in the absence of kinetic limitation.55 × 10−10 mol cm−2 (a).. much thicker (Γ = 2. 6. Bertotti / Electrochimica Acta 52 (2007) 2181–2188 2185 Fig.3 × 10−10 mol cm−2 (b). At this condition. substrate diffusion within the film and the cross-chemical reaction may determine the value of 1/I at 1/ω1/2 = 0.03 × 10−9 mol cm−2 ) at different rotation rates: 100 rpm (a).C. This supposition was investigated by performing an experiment with Prussian blue as surrogate film since Prussian blue film is electrocatalytically inactive towards the oxidation of deoxyguanosine. pointed out that we assume the morphology of this Prussian blue film to be unaffected by intercalation of Ru in the film. Hydrodynamic voltammograms (A) for a solution containing 1 mmol L−1 deoxyguanosine + 0. 10. 6).62nFAD2/3 ν−1/6 cs ω1/2 ) (8)  where ω is the rotation rate. as shows Fig. 7A shows Kouteck´y-Levich plots for four different RuOHCF thicknesses and the set of straight lines with positive intercepts suggests that limiting current at these modified electrodes is dependent on the dynamic features associated with the film. Fig. kME is the heterogeneous rate constant for the reaction between the catalyst and the substrate.18 V (b) 1. (8) to obtain kinetic information in this system. 5. the influence of mass-transport of deoxyguanosine to the film surface should be minimized. there are 10 possible cases to describe the mediation process in modified electrodes (Table 2). This second observation would suggest that the deoxyguanosine diffusion is rather facile within an open structure porous film and probably allows the substrate to react with the mediating centers throughout a large extent of the film thickness.25 V (d). 1. charge transport. 900 rpm (c).  data of log kME versus log Γ [47–49] were plotted as shown in Fig. In order to investigate the best situation that fits our experimental results.9 × 10−10 mol cm−2 (c) and 16. Supporting electrolyte: 0.5 mol L−1 NaNO3 + 0. 7C.L. It should be In order to obtain information on the limiting dynamic steps. D is the diffusion coefficient in the bulk solution and the other symbols have their usual significance. Accordingly. The positive intercept in each plot indicates a rate-determining step associated with the film that is not controlled by the mass transport of the substrate to the film/solution interface.

the whole layer participates in the reaction and this prediction confirms the above-mentioned observation (Fig. current is determined only by the rate of the cross-exchange reaction.  . Dashed lines represent the 95%  confidence limit. LS. M. Paix˜ao. In this case. k. The subscribed notation indicates whether kinetics (k) or mass-transport (ts or te (transport of reactant or electrons. The rate constant. k.L. reaction zone in the middle of the layer.05 mol L−1 HCl solution at RuOHCF modified electrodes with different Γ values: 9.9 × 10−10 mol cm−2 (c) and −10 −2 16. L (or Γ ) [47–49] Case notation Ets EkE LEts LEk LRZte ts LSte LSk  Expression for kME κDSP L κkE κDSP L Dct k cs Dct bo κDSP + Lcs L Dct bo Lcs √ κ kbo DSP κbo Sk Dct bo Lcs k bo Lk κkbo L Ste  Order of kME vs. . whose value can be determined from  the expression of kME in the Lk kinetic model:  kME = κkΓ (9) where κ is the partition coefficient of the substrate between film and solution.8 × 10 mol cm (d). 7. Kouteck´y-Levich plots (A) for oxidation of deoxyguanosine (1 mmol L−1 ) in a 0. was determined by Scheme 2. 11. throughout the layer. 6) on the free diffusion of the substrate into the RuOHCF film.55 × 10−10 mol cm−2 (a).2186 T. and order of k  kME ME vs.5 mol L−1 NaNO3 + 0. Fig. Bertotti / Electrochimica Acta 52 (2007) 2181–2188 Table 2 Equations defining the heterogeneous rate constant for the modified electrode. L (or Γ ) −1 0 −1 0 −1 −1 0 −1 0 1 The notation defines the location of the reaction into the film: L. respectively) controls the overall process. LRZ. near the electrolyte interface. near the electrode interface. According to this model. LE. 10. Panel B shows the dependence of current values at ω−1/2 = 0 on the surface excess (Γ ). which is close to the expected value = 1 for the Lk case.R.3 × 10−10 mol cm−2 (b). Values of log kME as a function of log Γ are shown in panel C.C.

J.F. Anal. 72 (2000) 3764. P. L. Mugweru. Srivastava. P. E. Z. Chem. P. Miranda-Ordieres.P. Rustling. Res. This seems to be the case in the anodic oxidation of deoxyguanosine at RuOHCF coatings and it may be concluded that increased quantities of the catalyst into the film do provide kinetic advantages because the diffusion of the substrate through RuOHCF layers is not restrained.P. Toxicol. P. Wu. .M. Brabec. J. 13 (2000) 601. E. Bioelectrochem. Dryhurst. J. k was found to be 3. Electroanalysis 16 (2004) 1193. Anal. Stuart. Chem. κ was considered to be 1 taking into account results presented in Fig. Hu. G. Chem. H. Electrochim. 8 (1997) 31. Analyst 127 (2002) 329.W. Linear Kouteck´y-Levich plots with straight lines possessing positive intercepts. J. Foord. Serrano.F. J. M. Brett. Anal. This value is significantly higher than the one calculated by taking into consideration the flux for the crossreaction (kΓ cs = 1. C. the slope corresponding to (nFA␬kΓ cs )−1 . A. Chem. M. Electroanalysis 18 (2006) 327. 119 (1997) 7388. Medeiros.47 × 10−9 mol cm−2 ) before the current becomes limited by the electron transfer rate. In the design of optimised electrocatalytic sensors. E. Anal. Farias.J. Chem.P. N.L. Qi.O. However. (iv) the rate of the catalytic (cross-exchange electron transfer) reaction. Electroanalysis 8 (1996) 7. Anal. 2187 The usefulness of the proposed modified electrode as a practical sensor for deoxyguanosine will be subject of further studies. ´ P. 68 (1996) 2629. Wang. Conclusions On evaluating the efficiency of coated electrodes some points should be taken into account such as: (i) diffusion of the substrate in the solution. J. Kelley.B. H. Electroanalysis 8 (1996) 15. J. Musameh. Toxicol. L. Further efforts will be directed now to evaluate the efficiency of this kind of electrochemical sensor to monitor at real time the formation of deoxyguanosine during biochemical processes involving damages in DNA. Berg. Brett.M. M. Hill. Farias. P. Chem. Shiraishi. The number of electrons in the electrodic process (n = 2) was calculated by using the slopes of the straight lines plotted in Fig. Nucleic Acids Res. H. A realistic comparison between the efficiency of the RuOHCF modified electrode with other deoxyguanosine sensors reported in literature such as carbon paste electrodes modified with cobalt hexacyanoferrate [53] or (tris(2. X. Acknowledgements Authors are thankful to Dr. A. Korri-Yousouli.H. 7A and the literature value of 3. Trends Biotechnol. G. Wu. Ferapontova.F. Yassar. J. Compton. Am. 2002. Chim. Analyst 128 (2003) 912.G. Dom´ımguez. Yang. From the slope of the straight line shown in Fig. Chem. J. F. 376 (2003) 205. Zhou. C. Soc. Z.S. J.F. Wang. Palecek. Anal.A. Rustling. Taking into account that the cross-exchange reaction occurs throughout the film and two electrons are involved in the anodic process.K. Biochemistry. Electroanal. Tu˜no´ n-Blanco.L. W. 74 (2002) 4044. G. substrate diffusion and delivery of charge. 15 (2002) 367. G. R. Mikkelsen. de-los-Santos-Alvarez. Livache. H. Rivas. Prado. Bioenerg.M. Garnier. J. A. Chung.D. Wang. A. Brabec.M.H. C.4 × 10−11 mol cm−2 s−1 ).01 cm2 s−1 ). Bioconjugate Chem.. 4. S. which are proportional to surface excess (Γ ) are an indication of the “Lk” case. (ii) propagation of electric charge through the film. 7B (Ik versus Γ plot). H. J. Anal. S. K. L. Chem. L. Am. Fei.W. Marken. V.G. It should be noticed that the concentration profile of the substrate is uniform throughout the film.A. (iii) penetration and diffusion of the substrate into the film. A. B. Thorp. Electroanalysis 7 (1995) 774. Pan. P.G. Petri for helping to perform film thickness measurements and to FAPESP (Fundac¸a˜ o de Amparo a` Pesquisa do Estado de S˜ao Paulo) and CNPq (Conselho Nacional de Desenvolvimento Cient´ıfico e Tecnol´ogico) for the financial support.U. Karber. Anal. F. J. Y. Karber. 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Estavillo.H.2 × 106 mol−1 L s−1 .S. a possible mechanism for the electrocatalytic reaction of deoxyguanosine is the formation of 8-oxo-deoxyguanosine in a two-electron [52] mechanism. L.H.L. N. the uniform use of a mediator throughout the coating is desirable because a high flux of substrate/analyte may be handled by the tridimensionally incorporated catalyst. F. R.E. Cheng. Roget.3 × 10−6 cm2 s−1 [50] for the diffusion coefficient of 8oxo-2 -deoxyguanosine in water (ν = 0. the results presented in this work associated with the response stability and the expressive current enhancement envisages the favorable application of the sensor for deoxyguanosine analysis. L. References [1] [2] [3] [4] [5] [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] V. S.A. Schenkman. rate constant values being in the range 104 –106 mol−1 L1 s−1 in these cases. Freeman. J. Chem. A. A. J. 125 (2003) 1431. Kawdu. P. G. J. Gr¨undler. M. C. 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