2015 Cinti
2015 Cinti
2015 Cinti
Full Paper
DOI: 10.1002/elan.201500168
Abstract: In this work a comparative study using Screen- electrochemically characterized. Nanoengineered SPEs
Printed Electrodes (SPEs) modified by drop casting with have been tested with ferricyanide, NADH, ascorbic acid
Carbon Black, Single Walled Carbon Nanotubes¢COOH, and cysteine. We observed valuable electroanalytical per-
Graphene Oxide, and reduced Graphene Oxide is report- formances of Carbon Black with the advantage to be i)
ed. The carbon nanomaterials employed were character- cost-effective ii) suitable to obtain stable and homoge-
ized by X-ray photoelectron and Raman spectroscopy, nous dispersion and iii) mass-producible following a well
while the modified SPEs have been morphologically and established route.
Keywords: Screen-printed electrode · Carbon black · Graphene · Carbon nanotubes · Drop casting
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strumentation upon necessity. Carbon ink is a suitable 2.3 SPE Preparation
platform to be modified with various kinds of material
e.g. nanomaterials, organic macromolecules or polymers, SPEs were produced with a 245 DEK (Weymouth, UK)
due to its the resistance to a wide range of solvents, low screen-printing machine. Graphite based ink (Electrodag
background current and broad potential windows of ap- 423 SS) from Acheson (Milan, Italy) was used to print
plication. However, the (nano)modified surface leads to the working and counter electrode. Silver ink (Electrodag
a specific electrocatalytic behaviour depending solely on 477 SS) was used to print the reference electrode. The
the nature of the modifier. This paper reports a morpho- substrate was a flexible polyester film (Autostat HT5) ob-
logical and electrochemical characterization of screen- tained from Autotype Italia (Milan, Italy). The diameter
printed electrodes (SPEs) nanoengineered by means of of the working electrode was 0.3 cm resulting in a geomet-
SWCNTs, graphene and CB. The different modified elec- ric area of 0.07 cm2.
trodes will be characterized by scanning electron micros-
copy (SEM), electrochemical impedance spectroscopy
2.4 Carbon Nanomaterial Dispersion
(EIS) and cyclic voltammetry (CV). Furthermore, all the
modified SPEs have been tested in the presence of sever- 2.4.1 Carbon Black Dispersion
al relevant molecules such as nicotinamide adenine dinu-
cleotide reduced (NADH), ascorbic acid (AA) and cys- The dispersion of CB was prepared by adding 10 mg of
teine, obtaining important information related to their an- CB powder to 10 mL of solvent (a mixture dimethylfor-
alytical performance. mamide (DMF) : water (1 : 1)) sonicated for 60 min at
59 kHz.
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2.5 Modification of Screen-Printed Electrodes
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that revealed in the case of reduced GO-SPE which is
constituted by few rGO aggregates (Figure 3j and 3k).
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Fig. 3. SEM micrographs of bare SPE (a-b), CBNPs-SPE (c-d), SWCNTs-O-SPE (e-g), GO-SPE (h-i) and rGO-SPE (j-k).
(R2 = 0.992), corresponding respectively to, CB-SPE, where Ip is the peak current, F is the Faraday constant, A
SWCNTs-O-SPE, rGO-SPE, GO-SPE and bare SPE. is the electrode area, D is diffusion coefficient of the ana-
Each SPE showed a linear response, indicating a diffusion- lyte, v is the scan rate, C is the concentration of the spe-
al process. Furthermore, associated with Nicholson Equa- cies and n is the number of electrons transferred in the
tion 1 is the Randles¢Ševcik Equation 2 [44] electrochemical process. In the case of semi-infinite diffu-
sion of the probe at the electrode surface, the analysis of
the cyclic voltammetry peaks in terms of the log Ip vs. log
v should consist in a slope equal to 0.5 in order to vali-
I p ¼ 0:4463 ðF 3 =RTÞ0:5 n1:5 AD0:5 Cv0:5 ð2Þ date both Equations1 and 2. The slopes of 0.55, 0.52, 0.37,
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Table 1. Electron transfer rate constants, cyclic voltammetric data, amperometric sensitivities and LOD for several compounds at
modified-SPEs.
Bare SPE CB-SPE SWCNTs-O-SPE GO-SPE rGO-SPE
k0 (cm/s) Fe(CN)64¢/3¢ – 0.00452 0.00251 0.00167 0.00247
DE (mV) Fe(CN)64¢/3¢ 430 80 100 130 120
Eox’ (mV) NADH 550 400 440 > 600 530
Sensitivity (mA/M cm2) NADH 4.32 224 281 – 88.5
LOD (mM) NADH 6 1 5 – 5
Eox’ (mV) AA 420 150 90 380 320
Sensitivity (A/M cm2) AA 3.98 278 496 19 203
LOD (mM) AA 7 1 5 3 2
Eox’ (mV) Cysteine 930 580 580 950 700
Sensitivity (A/M cm2) Cysteine 4.82 362 565 10.3 211
LOD (mM) Cysteine 30 1 5 24 6
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Fig. 6. Cyclic voltammograms obtained in phosphate buffer 0.05 M + KCl 0.1 M, pH 7.4 in absence (a) and in presence of NADH (b,
2 mM), ascorbic acid (c, 2 mM) and cysteine (d, 2 mM). All recorded at a scan rate of 50 mV/s using bare SPE (black line) or SPE
modified with CB (violet line), SWCNTs-O (red line), GO (blue line), rGO (green line). Equations related to NADH, ascorbic acid
and cysteine oxidation reactions are reported in the graph, respectively b, c and d.
value for bare SPE is much higher (Rct = 293.9 1.5 kW) capacitive current (Figure 6a) and by the longest time to
than those for the nanomodified SPE; in the latter case, reach the stabilization (Figure 7). Here, we studied the
the highest Rct is found for GO-SPE (Rct = 68.6 1.2 kW). detection of three important electroactive molecules in
The other sensors showed a Rct lower than 100 W, con- clinical and biochemical field: NADH, ascorbic acid and
firming the advantage to use the nanomodified SPE. cysteine.
The electrochemical oxidation of NADH is of great in-
3.3 Electroanalytical Sensing Towards NADH, Ascorbic terest because of its requirement in many biosensors
Acid and Cysteine based on dehydrogenase enzymes (about 300 dehydro-
genases are strictly dependent on the coenzyme and its
One of the great advantages to use carbon nanomaterial oxidized form NAD + ). Two critical issues are related to
to modify electrodes is easily attributable to their wide the high overpotential required to detect target mole-
potential window and high electrochemically accessible cules, and to monitor fouling problem.
area: the film physically or chemically deposited onto the Here, we studied the oxidation of NADH at the differ-
electrode surface, allows the measurement of molecules ent developed SPEs. As illustrated in Figure 6b SPEs
with relatively high oxidation potentials. As reported in modified with CB and SWCNTs-O show the lowest po-
Figure 6a, all the modified SPEs have wide operative po- tentials, respectively 400 and 440 mV. In comparison
tential windows when performing a background analysis rGO-SPE and GO-SPE show peak potentials of at
in phosphate buffer, ranging approximately from ¢0.3 to 530 mV and higher than 600 mV, respectively. The over-
1.0 V (vs. Ag/AgCl), a useful range in voltammetric anal- potentials achieved here are satisfactory and well-com-
ysis. However, it should be noted how SWCNTs-O-SPE, pare with other results found in literature where the same
if compared with other SPEs, is characterized by a larger nanomaterials are used as electrode modifier, highlighting
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proved. Many systems based on carbon nanomaterials
have been developed to detect these important biomole-
cules and the values shown in this work by CB-SPEs ac-
quire great analytical relevance. CB-SPE shows lower
overpotential than rGO-SPE and GO-SPE. As for
SWCNTs-O-SPE, the analytical performances are similar
to those of CB, also if the comparison is made with works
reported in literature [52, 53], but CB offers a very valua-
ble compromise considering performance and cost.
Based on the above cyclic voltammetric results, the typ-
ical amperometric responses of the different modified
SPEs were examined as a function of different concentra-
tions of NADH, ascorbic acid and cysteine. Ad hoc po-
tentials were applied to achieve the electrooxidation at
the different SPEs: 600, 150 and 400 mV were exploited,
respectively, to detect NADH, ascorbic acid and cysteine.
Figure 7 illustrates the amperograms obtained at the con-
centration range from 0 to 100 mM in phosphate buffer.
As expected, the SWCNTs-O and CB modified-SPEs dis-
play higher current response to the addition of the ana-
lytes compared to the other SPEs.
In Table 1 overpotentials, sensitivities and LOD ob-
tained by using the different carbon nanomaterial as
SPEs modifying tools were reported: although SWCNTs-
O-SPE was capable to yield the best sensitivities, CB-SPE
reached the lowest LOD (calculated as S/N = 3) confirm-
ing its excellent electrocatalytic properties.
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