Article

Cite This: ACS Appl. Nano Mater. 2019, 2, 7311−7318 www.acsanm.org

A Novel Electrochemical Sensor Based on Metal Ion Infiltrated Block

Copolymer Thin Films for Sensitive and Selective Determination of
Dopamine
Salih Zeki Bas,† Cian Cummins,‡ Andrew Selkirk,‡ Dipu Borah,‡ Mustafa Ozmen,†
and Michael A. Morris*,‡
†
Department of Chemistry, Selcuk University, 42250 Konya, Turkey
‡
AMBER Centre and CRANN, Trinity College Dublin, Dublin 2, Ireland
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
Downloaded via UNIV OF EXETER on July 16, 2020 at 18:38:09 (UTC).

ABSTRACT: An electrochemical sensor using copper oxide nanodots (CuO nanodots−ITO) developed from a block
copolymer template is demonstrated for sensitive and selective determination of dopamine (DA). The current signal of CuO
nanodots−ITO was linear with the concentration of DA in the range between 0.12 and 56.87 μM (R = 0.9975) with a
sensitivity of 326.91 μA mM−1 cm−2 and a detection limit of 0.03 μM. Furthermore, the anti-interference ability of the present
sensor to possible interfering substances including ascorbic acid, uric acid, acetaminophen, epinephrine, hydrogen peroxide,
phenol, catechol, hydroquinone, and some inorganic compounds has been investigated. Our work highlights the significance of
using a bottom-up nanofabrication technique to create a robust and reliable dopamine sensor that has critical importance in
neurological disorders.
KEYWORDS: dopamine, electrochemical sensor, copper oxide, block copolymers, infiltration process

1. INTRODUCTION these difficulties, there is still a need to develop novel materials

Dopamine (3,4-dihydroxyphenylethylamine, DA) is a crucial
catecholamine neurotransmitter that plays a critical role in the
brain, central nervous, renal, hormonal, and cardiovascular
system.1 An abnormal DA level causes various neurological
disorders such as schizophrenia as well as Huntington’s and
Parkinson’s disease.2 Therefore, since it was discovered in the
late 1950s,3 many researchers have striven to develop simple
yet precise methods for DA detection. Methods including
spectroscopic and colorimetric among others have been
reported for analyzing DA.4−9 In addition, DA can be detected
electrochemically because of its electrochemical activity.
However, DA coexists with other electroactive molecules
such as e.g. ascorbic acid and uric acid in biological samples,
and the oxidation peak of DA can be overlapped with those of
ascorbic acid and uric acid in conventional electrochemical
methods, thus resulting in poor selectivity and sensitivity in DA
determination.1,2,10 Although various electrode-modified ma-
terials11−15 have been reported in the literature to overcome
for precise DA determination.
For this purpose, we developed an electrochemical sensor
via infiltration of block copolymers (BCPs) with copper nitrate
to fabricate nanoscale copper oxide nanodots for accurate DA
determination. The motivation for this work is based upon
promising reports of nanoscale CuO for sensing DA.16,17
Furthermore, our previous work on nanoscale Fe3O4 for
electrochemical sensing revealed enhanced sensing of hydro-
gen peroxide even in the presence of interferents.18 BCPs are a
macromolecular species composed of two covalently bond
polymers in their simplest form. A di-BCP can produce
morphologies including spherical, cylindrical, gyroidal, and
lamellar phases.19 The morphologies can be tailored through
tuning of the BCP volume fraction, while the feature
dimensions are related to overall BCP molecular weight.20
Received: September 18, 2019
Accepted: November 5, 2019
Published: November 5, 2019

© 2019 American Chemical Society 7311 DOI: 10.1021/acsanm.9b01794

ACS Appl. Nano Mater. 2019, 2, 7311−7318
ACS Applied Nano Materials
Scheme 1. Process for Developing CuO Nanodots on ITO and Mechanism of DA Detection on CuO Nanodots−ITO
Thus, BCPs provide a versatile platform for nanoapplications.
Recent reviews are available on the wide-ranging thin film uses
in for example nanoelectronics,21 nanophotonics,22 and
energy.23 Moreover, infiltrating one BCP domain selectively
enables the formation of various metallic, metal oxide,
insulator, or ceramic features with a plethora of uses.24 To
successfully infiltrate a BCP domain, a judicious choice of the
neat BCP is required. For example, PS-b-PEO and PS-b-PxVP
(x = 2 or 4) are routinely chosen for solution based infiltration
processes25,26 (as used in this article).
The voltametric behavior of the oxidation reaction of DA on
CuO nanodots−ITO was studied by using cyclic voltammetry
(CV) and differential pulse voltammetry (DPV) techniques.
The sensing performance of CuO nanodots−ITO, i.e., linear
work range, limit of detection limit (LOD), sensitivity,
selectivity, repeatability, and storage stability, is described.
The performance of the CuO nanodots progresses further the
possibility of utilizing BCP nanofabrication methods that are
low cost and scalable over large wafer sizes.
2. MATERIALS AND METHODS
2.1. Reagents. Dopamine hydrochloride, acetaminophen (Ac),
epinephrine (Ep), catechol (CC), hydroquinone (HQ), phenol, and
D-(+)-glucose were obtained from Sigma-Aldrich. KCl (99%), MgCl2
(99%), NaH2PO4, Na2HPO4, NaOH, H3PO4 (89%), NaCl (99.5%),
Zn(NO3)2 (98.5%) (extra pure), Cu(NO3)2, tetrahydrofuran (THF)
(99.8%, anhydrous), H2O2 solution (30%, extra pure), ethanol
(EtOH, dehydrated), toluene (99.8%, anhydrous) (from Merck),
ascorbic acid (AA, from J.T. Baker), uric acid (UA, from Alfa Aesar,
99%), and CaCl2 (from Riedel, 99%) were obtained. For all aqueous
solutions, a Millipore Milli-Q Plus water purification system (R = 18.2
MΩ·cm at 25 °C) was used. Indium tin oxide (ITO)-coated glass
slides (surface resistivity: 8−12 Ω/sq) were obtained from Sigma-
Aldrich. Poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) was
purchased from Polymer Source, Inc., Canada, with a molecular
weight of Mn = 33.5 kg mol−1 (Mn.PS = 24 kg mol−1 ; Mn,P4VP = 9.5 kg
mol−1, f PS = 0.70) and a polydispersity (Mw/Mn) of 1.15, where Mn
and Mw are number-average and weight-average molecular weights,
respectively.
2.2. Apparatus and Instrumentation. A Model CHI-660C
electrochemical analyzer (CH Instruments Co., USA) was employed
for all electrochemical studies. The electrochemical measurements
were performed by using a three-electrode system, including CuO
nanodots−ITO (working electrode), platinum wire (auxiliary
electrode), and Ag/AgCl electrode in saturated KCl solution
(reference electrode). The buffer solution in the cell was saturated
with nitrogen for 20 min to obtain a N2-saturated solution before CV
and DPV measurements. Atomic force microscopy (AFM) (Park
7312
Article
Systems, XE-100) was operated in ac (tapping) mode under ambient
conditions by using silicon microcantilever probe tips with a force
constant of 42 N m−1. X-ray photoelectron spectroscopy (XPS)
studies were performed on a VG Scientific ECSAlab Mk II system
using Al Kα X-rays (1486.6 eV) under ultrahigh-vacuum conditions
(<5 × 10−10 mbar). The analyzer pass energy for all survey spectra
recorded was 100 eV while high-resolution scans were processed with
pass energy set to 20 eV.
3. RESULTS AND DISCUSSION
3.1. CuO Nanodots−ITO Sensor Fabrication. The
process employed to develop CuO nanodots atop ITO as
the working electrode in this work is illustrated in Scheme 1.
Note we have previously reported a similar process for the
fabrication of iron oxide nanodots for the detection of
hydrogen peroxide and readers are referred to that paper for
further details on the nanofabrication steps.18 Briefly, after
deposition of PS-b-P4VP on ITO substrates, solvent vapor
annealing was performed to improve lateral order of micro-
domains. The P4VP microdomains of PS-b-P4VP were then
swollen selectively in EtOH to create a porous nanodot
template. This was followed by the spin coating of a copper
nitrate solution atop the porous template and treated in a UV/
O3 atmosphere to yield CuO nanodots.
Because of the rough surface nature of ITO as well as the
interaction of CuO in affecting film formation, a representative
atomic force microscope (AFM) is shown in Figure 1 of CuO
nanodot formation on a silicon substrate. Well-defined
nanodots, with center-to-center spacing of 26 nm and dot
diameter of 20 nm, were produced by using this process. The
process employed was transferred to ITO substrates with
different concentrations of copper nitrate precursor.
3.2. Electrochemical Behaviors of Bare ITO, PS-b-
P4VP/ITO, and CuO Nanodots−ITO. The electrochemical
performance of CuO nanodots−ITO prepared with 0.5 wt %
CuO toward DA was compared with those of other ITO
electrodes (bare ITO and PS-b-P4VP/ITO). Figure 2 shows
CV of bare ITO (curve I) and PS-b-P4VP/ITO (curves II and
III) in the presence of 25 μM DA in N2-saturated 0.1 M PBS at
pH 7.4. As illustrated in curves I and II of Figure 2a, there is no
oxidation peak sighted at bare ITO and PS-b-P4VP/ITO in the
presence of DA in the range of potentials from 0 to 0.6 V. In
curve III of Figure 2a, CV of CuO nanodots−ITO displays an
oxidation peak at 0.16 V, which roots in the oxidation of DA to
dopamine−o-quinone.27 This observation demonstrated that
CuO nanodots−ITO has excellent electrocatalytic activity to
DOI: 10.1021/acsanm.9b01794
ACS Appl. Nano Mater. 2019, 2, 7311−7318
ACS Applied Nano Materials
Figure 1. AFM image of CuO nanodots on silicon substrate produced
by using a PS-b-P4VP and copper nitrate infiltration process.
Figure 2. (a) CVs of bare ITO (curve I), PS-b-P4VP/ITO (curve II)
and CuO nanodots-ITO (curve III) in the presence of 25 μM DA in
0.1 M PBS (pH 7.4). (b) CVs of CuO nanodots-ITO in the presence
of 5 μM (curve I), 10 μM (curve II), 15 μM (curve III) DA at scan
rate of 50 mV s−1.
7313
Article
the electrochemical oxidation of DA. Also, the peak signal
obtained with CuO nanodots−ITO was substantially higher
than those obtained with bare ITO and PS-b-P4VP/ITO
electrodes, indicating that CuO nanodots play a crucial role in
increasing the electroactive surface area of CuO nanodots−
ITO. The electrochemical catalytic activity of CuO nanodots−
ITO toward DA was studied by the CV technique in the
presence of various concentrations of DA in 0.1 M PBS at pH
7.4 (Figure 2b). The anodic current signals of CuO nanodots−
ITO increased proportionally with increasing the concen-
tration of DA solution from 5 to 15 μM because of the
electrochemical oxidation reaction of DA on CuO nanodots−
ITO. In addition, the pH effect on the current signal of 5 μM
DA at CuO nanodots−ITO was studied in a range of pH 5.0−
9.0. The results show that the highest current was obtained at
pH 7.4. A 0.1 M PBS (pH 7.4) solution was used in
subsequent electrochemical studies.
3.3. Effect of CuO Concentration. The CuO concen-
tration was investigated to elucidate the possibility of
enhancing DA sensor performance. The effect of CuO
concentration on the current signal of CuO nanodots−ITO
in 0.1 M PBS containing 25 μM DA was tested by using the
electrodes prepared with three different concentrations of Cu
(0.5, 1.5, and 3 wt %). Figure 3 displays the AFM images of
ITO surfaces after self-assembly of PS-b-P4VP and deposition
of 0.5, 1.5, and 3 wt % solutions. While our approach with this
particular PS-b-P4VP and CuO metal ion inclusion produced a
sensor with good performance as discussed later, nanostruc-
tures observed appear difficult to control. (Note that other
BCP systems that allow improved definition of nanostructures
will be reported in due course.) Therefore, since the AFM
images of all concentrations prepared appear similar, XPS was
performed to examine atomic percentage of CuO present. We
do note that large areas of CuO deposit are observed at higher
precursor concentrations (as seen in a previous report26),
suggesting a decrease of surface area and hence the poor
sensitivity to DA for 3 wt % compared to 0.5 wt %. XPS was
also used to confirm the chemical nature of the CuO nanodots
following deposition and UV/O3 treatment.
Figure 4 displays the survey spectrum and high-resolution
spectra of the Cu 2p region for 0.5 (a), 1.5 (b), and 3 wt % (c).
From the survey spectra (a, b, c), we observe Sn, In, and O that
are attributed to the substrate material. CuO peaks are revealed
by high-resolution scans of the Cu 2p region for Cu-treated
samples (inset in Figure 4a). We see the characteristic
elemental Cu 2p at ∼933 eV.28 Moreover Cu2+ satellites are
revealed at ∼942 and ∼963 eV, confirming the formation of
CuO.
We observed an increase in the atomic percentage of Cu of
just over 2% between the 0.5 and 1.5 wt % samples (from 5.79
to 7.86 Cu atomic %), while an incremental increase (∼0.7%)
is found between 1.5 and 3 wt %. The small increase between
the 1.5. and 3 wt % shows we have reached a saturation point
in the inclusion process. This is related to the size of the
domains, at ∼20 nm, and the relative thinness of the original
PS-b-P4VP film, at ∼25 nm. While we comment on the
physical characteristics that reveal an upper saturation point, it
is interesting to observe that the 3 wt % sample does not reveal
an enhancement in sensing as mentioned earlier. It is shown
through a series of experiments that 0.5 wt % samples
produced the best results for sensing DA. As illustrated in
Figure 5, the largest value was obtained in the current signal of
CuO nanodots−ITO prepared with 0.5 wt % CuO, and then
DOI: 10.1021/acsanm.9b01794
ACS Appl. Nano Mater. 2019, 2, 7311−7318
ACS Applied Nano Materials
Figure 3. AFM topography images of CuO nanodots on ITO after deposition of (a) 0.5, (b) 1.5, and (c) 3 wt % on PS-b-P4VP template followed
by UV/O3 treatment.
Figure 4. Survey XPS spectra of samples treated with 0.5 (a), 1.5 (b), and 3 wt % (c). Inset in (a) shows core level spectra of Cu 2p.
Figure 5. DPVs of CuO nanodots−ITO prepared with three different
concentrations of CuO (0.5, 1.5, and 3 wt %) in 0.1 M PBS
containing 5 μM DA.
the current signal decreased with further increasing CuO
concentration. This result may be attributed to the fact that
increasing concentration of CuO reduces the electroactive
surface area of the sensor due to the large-sized CuO nanodots
and areas of large deposits on the surface of CuO nanodots−
ITO and affects negatively the electrocatalytic activity toward
the oxidation reaction of DA.29−34 According to this result,
further studies were performed using CuO nanodots−ITO
prepared with 0.5 wt % CuO.
7314
Article
3.4. Analytical Characteristics of CuO Nanodots−ITO.
The DPV technique was used to estimate the analytical
characteristics at CuO nanodots−ITO for DA detection
because of its higher current sensitivity compared with CV.
Figure 6a shows the DPV signals at the CuO nanodots−ITO
for different concentrations of DA. Obviously, a stepped
increase in the current signal of DA was sighted with stepped
increasing of DA concentration, which indicates that CuO
nanodots−ITO can catalyze electrochemically the oxidation of
dopamine to dopamine−o-quinone. Figure 6b shows the
changes in the response currents of CuO nanodots−ITO as a
function of DA concentration. The statistical analysis of the
calibration curve gave the following equation: IDA (μA) =
0.0368 + 0.0356CDA (μM) (R = 0.9975), where CDA is the
concentration of DA and IDA is the current signal of DA. The
DPV response of CuO nanodots−ITO reveals linearity in the
range of 0.12−56.87 μM DA. The limit of detection (LOD)
was calculated to be 0.03 μM DA, according to the formula
3SD/m, in which m is the slope of the calibration graph and
SD is the standard deviation calculated from the DPV signals
of 0.36 μM DA for five times.35 The current sensitivity was
found to be 326.91 μA mM−1 cm−2 to DA for CuO nanodots−
ITO. The analytical characteristics of CuO nanodots−ITO was
compared with other DA sensors presented in the literature
and are summarized in Table 1. It can be seen that the present
sensor has satisfactory linear work range and LOD for the
electrochemical detection of DA and shows that simple and
low-cost bottom-up nanofabrication methods can be utilized
for sensing purposes.
DOI: 10.1021/acsanm.9b01794
ACS Appl. Nano Mater. 2019, 2, 7311−7318
ACS Applied Nano Materials Article

chemical measurements.46,47 Figures 7a and 7b show DPVs of

Figure 6. (a) DPVs of CuO nanodots−ITO in the presence of various
concentrations (0.12−56.87 μM) in pH 7.4 PBS. (b) Calibration
graph of CuO nanodots−ITO for determination of DA (n = 3).
3.5. Interference Study. To evaluate the selectivity of the
presented sensor, the interference effects of ascorbic acid
(UA), uric acid (UA), acetaminophen (Ac), epinephrine (Ep),
D(+)-glucose (Glu), phenol (Ph), catechol (CC), hydro-
quinone (HQ), H2O2, CaCl2, MgCl2, Zn(NO3)2, NaCl, and
KCl were examined by using the DPV technique in 0.1 M PBS.
Especially, AA and UA, which are electroactive substances,
coexist with DA in the central nervous systems, and they can
be oxidized at a potential near that of neurotransmitters like
DA, resulting in an overlapping signal during the electro-
CuO nanodots−ITO in the presence of 1 mM CaCl2, 1 mM
MgCl2, 1 mM Zn(NO3)2, 1 mM NaCl, 1 mM KCl, 0.8 mM
AA, 0.2 mM UA, 1 mM D(+)-glucose, 1 mM Ph, and 1 mM
H2O2. It can be seen that the oxidation peaks of AA and UA
did not appear in the potential range of −0.1 to 0.3 V. No
significant reponses were observed with the addition of other
compounds, indicating a high selectivity of CuO nanodots−
ITO for the electrochemical determination of DA. In addition
to this, the oxidation behaviors of CC (2.5 μM) and HQ (2.5
μM) as structural analogues were compared with the current
response of DA by using the DPV technique. As shown in
Figure 7c, CuO nanodots−ITO exhibited the oxidation signals
for both substances in the same potential range of −0.1 to 0.3
V. But DA, a neurotransmitter in the central nervous system,
generally does not coexist with HQ and CC.48 CC (1,2-
dihydroxybenzene) and HQ (1,4-dihydroxybenzene), two
isomers of dihydroxybenzene compounds, often coexist in
environmental samples as pollutants.49 In Figure 7d, the
interference effects of Ac (2.5 μM) and Ep (2.5 μM) at CuO
nanodots−ITO were examined under similar conditions. The
DPV peak of Ac (−0.14 V) is quite far from that of DA. The
DPV peak of Ep is obtained at 0.24 V, indicating the peak-to-
peak separation (about 0.17 V) of the peak potentials between
DA and Ep is sufficiently large for the electrochemical
detection of DA. These findings show also that CuO
nanodots−ITO has also an anti-interference ability toward
Ac and Ep.
3.6. Repeatability and Stability. To determine the
repeatability of CuO nanodots−ITO, the current responses
to 2.5 μM DA were monitored for five times by using the same
electrode by the DPV technique. RSD was found to be 1.18%,
indicating an excellent repeatability of CuO nanodots−ITO.
The stability of CuO nanodots−ITO was examined by
monitoring the current response of 2.5 μM DA for three
electrodes prepared under the same conditions during 25 days.
After each experiment, CuO nanodots−ITO were thoroughly
washed with deionized water and used for examination in the
following experiment. The electrochemical results for the
stability of CuO nanodots−ITO are illustrated in Figure 8,
where i0 is the first current signal of CuO nanodots−ITO
newly prepared, i is the current signal at any storage time, and i
− i0 is the current change at any storage time. As illustrated in

Table 1. A Comparison of Analytical Characteristics of DA Sensing Systems

electrodea technique linear range (μM) LOD (μM) ref
PXa/Au/Cu-TCPP/GCE DPV 5−125 1 36
3D N-doped graphene DPV 3−100 1 37
GCE/N-rGO-180-8/NH3 DPV 0.5−150 0.41 38
MoS2PANI/rGO/GCE DPV 5.0−500 0.70 39
cs-SWCNT-IL/SPCE DPV 0.50−30 0.16 40
Fe3O4−NH2@GS/GCE DPV 0.2−38 0.126 41
PEDOT/Au DPV 0.2−300 0.1 42
PEDOT-LSG DPV 1−150 0.33 43
γ-WO3/GCE DPV 0.1−50, 50−600 0.024 44
PDEA-MWCNT/GO/GCE DPV 0.06−4.2, 4.2−18.2 0.042 45
CuO nanodots−ITO DPV 0.12−56.87 0.03 present work

a
CD-PNIPAM: β-cyclodextrin−poly(N-isopropylacrylamide); e-FGP: exfoliated flexible graphite paper; MIP: molecularly imprinted polymer;
PXa: poly(xanthurenic acid); TCPP: (4-carboxyphenyl)porphyrin; PANI: polyaniline; GSCR-MIPs: graphene sheets/Congo red-molecular
imprinted polymers; IL: ionic liquid; LSG: laser-scribed graphene; γ-WO3: monoclinic tungsten trioxide; PDEA: poly(N,N-diethylacrylamide);
GO: graphene oxide.

7315 DOI: 10.1021/acsanm.9b01794

ACS Appl. Nano Mater. 2019, 2, 7311−7318
ACS Applied Nano Materials Article

Figure 7. (a) DPVs of CuO nanodots−ITO with addition of 2 mM CaCl2, 2 mM MgCl2, 2 mM Zn(NO3)2, 2 mM NaCl, and 2 mM KCl; (b) 0.8
mM AA, 0.2 mM UA, 2 mM Glu, 2 mM Ph, and 2 mM H2O2; (c) 2.5 μM CC, 2.5 μM HQ, and 2.5 μM DA; and (d) 2.5 μM Ac and 2.5 μM Ep in
0.1 M PBS.

catalytic activity toward the electrooxidation of DA. CuO

nanodots provide a high specific surface area to both increase
sensing performance and improve the electrical conductivity of
the fabricated sensor. The linear work range for the
determination of DA was found to be 0.12−56.87 μM with
detection limits of 0.8 μM. Also, DPV measurements revealed
CuO nanodots−ITO possesses a strong anti-interference
ability in the presence of some common interferents. In
consideration of sensing ability, this novel platform is a robust
demonstration for fabricating a selective and sensitive sensor
for determination of dopamine in human metabolism.

■ AUTHOR INFORMATION
Corresponding Author
*(M.A.M.) E-mail morrism2@tcd.ie.
Figure 8. Stability of CuO nanodots−ITO (each data point is based
on monitoring the current signal of 2.5 μM DA in 0.1 M PBS at pH ORCID
7.4). Cian Cummins: 0000-0001-6338-3991
Andrew Selkirk: 0000-0002-1845-7100
Figure 8, CuO nanodots−ITO has a good stability for 6 days,
Dipu Borah: 0000-0002-2079-5707
and the signal of CuO nanodots−ITO retained about 98% of Mustafa Ozmen: 0000-0001-5117-9168
its first response. After 12 days, the current signal of CuO Michael A. Morris: 0000-0001-8756-4068
nanodots−ITO decreased by about 22%. Notes
The authors declare no competing financial interest.
4. CONCLUSIONS
In this study, we have successfully fabricated a novel DA sensor
by using CuO nanodots from a BCP template for selective
■ ACKNOWLEDGMENTS
Financial support was provided by the EU FP7 NMP project,
determination of dopamine, which displays noticeable electro- LAMAND (Grant 245565) project, and the Science
7316 DOI: 10.1021/acsanm.9b01794
ACS Appl. Nano Mater. 2019, 2, 7311−7318
ACS Applied Nano Materials
Foundation Ireland (Grant 09/IN.1/602) and is gratefully
acknowledged. The electrochemical part of this study was
supported by the Scientific Research Projects of Selcuk
University (Project No. 15401015).
■
REFERENCES
(1) Yang, S.; Yin, Y.; Li, G.; Yang, R.; Li, J.; Qu, L. Immobilization of
gold nanoparticles on multi-wall carbon nanotubes as an enhanced
material for selective voltammetric determination of dopamine. Sens.
Actuators, B 2013, 178, 217−221.
(2) Zhou, C.; Li, S.; Zhu, W.; Pang, H.; Ma, H. A sensor of a
polyoxometalate and Au−Pd alloy for simultaneously detection of
dopamine and ascorbic acid. Electrochim. Acta 2013, 113, 454−463.
(3) Wightman, R. M.; May, L. J.; Michael, A. C. Detection of
dopamine dynamics in the brain. Anal. Chem. 1988, 60 (13), 769A−
779A.
(4) Szopa, J.; Wilczyński, G.; Fiehn, O.; Wenczel, A.; Willmitzer, L.
Identification and quantification of catecholamines in potato plants
(Solanum tuberosum) by GC−MS. Phytochemistry 2001, 58 (2),
315−320.
(5) Carrera, V.; Sabater, E.; Vilanova, E.; Sogorb, M. A. A simple and
rapid HPLC−MS method for the simultaneous determination of
epinephrine, norepinephrine, dopamine and 5-hydroxytryptamine:
Application to the secretion of bovine chromaffin cell cultures. J.
Chromatogr. B: Anal. Technol. Biomed. Life Sci. 2007, 847 (2), 88−94.
(6) Li, Q.; Li, J.; Yang, Z. Study of the sensitization of tetradecyl
benzyl dimethyl ammonium chloride for spectrophotometric
determination of dopamine hydrochloride using sodium 1,2-
naphthoquinone-4-sulfonate as the chemical derivative chromogenic
reagent. Anal. Chim. Acta 2007, 583 (1), 147−152.
(7) Guo, Z.; Dong, S. Electrogenerated Chemiluminescence
Determination of Dopamine and Epinephrine in the Presence of
Ascorbic Acid at Carbon Nanotube/Nafion-Ru(bpy) Composite Film
Modified Glassy Carbon Electrode. Electroanalysis 2005, 17 (7), 607−
612.
(8) Vuorensola, K.; Sirén, H.; Karjalainen, U. Determination of
dopamine and methoxycatecholamines in patient urine by liquid
chromatography with electrochemical detection and by capillary
electrophoresis coupled with spectrophotometry and mass spectrom-
etry. J. Chromatogr. B: Anal. Technol. Biomed. Life Sci. 2003, 788 (2),
277−289.
(9) Moghadam, M. R.; Dadfarnia, S.; Shabani, A. M. H.;
Shahbazikhah, P. Chemometric-assisted kinetic−spectrophotometric
method for simultaneous determination of ascorbic acid, uric acid,
and dopamine. Anal. Biochem. 2011, 410 (2), 289−295.
(10) Cai, W.; Lai, T.; Du, H.; Ye, J. Electrochemical determination
of ascorbic acid, dopamine and uric acid based on an exfoliated
graphite paper electrode: A high performance flexible sensor. Sens.
Actuators, B 2014, 193, 492−500.
(11) Khudaish, E. A.; Al-Ajmi, K. Y.; Al-Harthi, S. H. A solid-state
sensor based on ruthenium (II) complex immobilized on polytyr-
amine film for the simultaneous determination of dopamine, ascorbic
acid and uric acid. Thin Solid Films 2014, 564, 390−396.
(12) Elhag, S.; Ibupoto, Z. H.; Liu, X.; Nur, O.; Willander, M.
Dopamine wide range detection sensor based on modified Co3O4
nanowires electrode. Sens. Actuators, B 2014, 203, 543−549.
(13) Wang, G. F.; Sun, J. G.; Zhang, W.; Jiao, S. F.; Fang, B.
Simultaneous determination of dopamine, uric acid and ascorbic acid
with LaFeO3 nanoparticles modified electrode. Microchim. Acta 2009,
164, 357−362.
(14) Atta, N. F.; Galal, A.; Ahmed, R. A. Poly(3,4-ethylene-
dioxythiophene) electrode for the selective determination of
dopamine in the presence ofsodium dodecyl sulfate. Bioelectrochem-
istry 2011, 80 (2), 132−141.
(15) Liu, Y.; Huang, J.; Hou, H.; You, T. Simultaneous
determination of dopamine, ascorbic acid and uric acid with
electrospun carbon nanofibers modified electrode. Electrochem.
Commun. 2008, 10 (10), 1431−1434.
7317
Article
(16) Reddy, S.; Kumara Swamy, B. E.; Jayadevappa, H. CuO
nanoparticle sensor for the electrochemical determination of
dopamine. Electrochim. Acta 2012, 61, 78−86.
(17) Yadav, P.; Manivannan, S.; Kim, H.-S.; Pandey, K.; Kim, K.;
Kim, J. Electrochemical Properties of Highly Sensitive and Selective
CuO Nanostructures Based Neurotransmitter Dopamine Sensor.
Electroanalysis 2017, 29 (9), 2106−2113.
(18) Bas, S. Z.; Cummins, C.; Borah, D.; Ozmen, M.; Morris, M. A.
Electrochemical Sensing of Hydrogen Peroxide Using Block
Copolymer Templated Iron Oxide Nanopatterns. Anal. Chem. 2018,
90 (2), 1122−1128.
(19) Bates, F. S.; Fredrickson, G. H. Block copolymers - Designer
soft materials. Phys. Today 1999, 52 (2), 32−38.
(20) Morris, M. A. Directed self-assembly of block copolymers for
nanocircuitry fabrication. Microelectron. Eng. 2015, 132, 207−217.
(21) Cummins, C.; Morris, M. A. Using block copolymers as
infiltration sites for development of future nanoelectronic devices:
Achievements, barriers, and opportunities. Microelectron. Eng. 2018,
195, 74−85.
(22) Stefik, M.; Guldin, S.; Vignolini, S.; Wiesner, U.; Steiner, U.
Block copolymer self-assembly for nanophotonics. Chem. Soc. Rev.
2015, 44, 5076.
(23) Yoo, H. G.; Byun, M.; Jeong, C. K.; Lee, K. J. Performance
Enhancement of Electronic and Energy Devices via Block Copolymer
Self-Assembly. Adv. Mater. 2015, 27 (27), 3982−3998.
(24) Cummins, C.; Ghoshal, T.; Holmes, J. D.; Morris, M. A.
Strategies for Inorganic Incorporation using Neat Block Copolymer
Thin Films for Etch Mask Function and Nanotechnological
Application. Adv. Mater. 2016, 28 (27), 5586−618.
(25) Cummins, C.; Bell, A. P.; Morris, M. A. Creating Active Device
Materials for Nanoelectronics Using Block Copolymer Lithography.
Nanomaterials 2017, 7 (10), 304.
(26) Ghoshal, T.; Shaw, M. T.; Bolger, C. T.; Holmes, J. D.; Morris,
M. A. A general method for controlled nanopatterning of oxide dots: a
microphase separated block copolymer platform. J. Mater. Chem.
2012, 22 (24), 12083−12089.
(27) Yu, D.; Zeng, Y.; Qi, Y.; Zhou, T.; Shi, G. A novel
electrochemical sensor for determination of dopamine based on
AuNPs@SiO2 core-shell imprinted composite. Biosens. Bioelectron.
2012, 38 (1), 270−277.
(28) Biesinger, M. C. Advanced analysis of copper X-ray
photoelectron spectra. Surf. Interface Anal. 2017, 49 (13), 1325−1334.
(29) Wu, H.; Wang, J.; Kang, X.; Wang, C.; Wang, D.; Liu, J.; Aksay,
I. A.; Lin, Y. Glucose biosensor based on immobilization of glucose
oxidase in platinum nanoparticles/graphene/chitosan nanocomposite
film. Talanta 2009, 80 (1), 403−406.
(30) Lu, G.; Zangari, G. Electrodeposition of platinum nanoparticles
on highly oriented pyrolitic graphite: Part II: Morphological
characterization by atomic force microscopy. Electrochim. Acta 2006,
51 (12), 2531−2538.
(31) Topçu Sulak, M.; Gökdoğan, Ö .; Gülce, A.; Gülce, H.
Amperometric glucose biosensor based on gold-deposited poly-
vinylferrocene film on Pt electrode. Biosens. Bioelectron. 2006, 21 (9),
1719−1726.
(32) Baş, S. Z.; Gülce, H.; Yıldız, S.; Gülce, A. Amperometric
biosensors based on deposition of gold and platinum nanoparticles on
polyvinylferrocene modified electrode for xanthine detection. Talanta
2011, 87, 189−196.
(33) Karimi-Maleh, H.; Fakude, C. T.; Mabuba, N.; Peleyeju, G. M.;
Arotiba, O. A. The determination of 2-phenylphenol in the presence
of 4-chlorophenol using nano-Fe3O4/ionic liquid paste electrode as an
electrochemical sensor. J. Colloid Interface Sci. 2019, 554, 603−610.
(34) Khodadadi, A.; Faghih-Mirzaei, E.; Karimi-Maleh, H.;
Abbaspourrad, A.; Agarwal, S.; Gupta, V. K. A new epirubicin
biosensor based on amplifying DNA interactions with polypyrrole and
nitrogen-doped reduced graphene: Experimental and docking
theoretical investigations. Sens. Actuators, B 2019, 284, 568−574.
(35) Villalonga, R.; Díez, P.; Eguílaz, M.; Martínez, P.; Pingarrón, J.
M. Supramolecular Immobilization of Xanthine Oxidase on Electro-
DOI: 10.1021/acsanm.9b01794
ACS Appl. Nano Mater. 2019, 2, 7311−7318
ACS Applied Nano Materials Article

polymerized Matrix of Functionalized Hybrid Gold Nanoparticles/

Single-Walled Carbon Nanotubes for the Preparation of Electro-
chemical Biosensors. ACS Appl. Mater. Interfaces 2012, 4 (8), 4312−
4319.
(36) Qiu, Z.; Yang, T.; Gao, R.; Jie, G.; Hou, W. An electrochemical
ratiometric sensor based on 2D MOF nanosheet/Au/polyxanthurenic
acid composite for detection of dopamine. J. Electroanal. Chem. 2019,
835, 123−129.
(37) Feng, X.; Zhang, Y.; Zhou, J.; Li, Y.; Chen, S.; Zhang, L.; Ma,
Y.; Wang, L.; Yan, X. Three-dimensional nitrogen-doped graphene as
an ultrasensitive electrochemical sensor for the detection of
dopamine. Nanoscale 2015, 7 (6), 2427−2432.
(38) Wiench, P.; González, Z.; Menéndez, R.; Grzyb, B.; Gryglewicz,
G. Beneficial impact of oxygen on the electrochemical performance of
dopamine sensors based on N-doped reduced graphene oxides. Sens.
Actuators, B 2018, 257, 143−153.
(39) Li, S.; Ma, Y.; Liu, Y.; Xin, G.; Wang, M.; Zhang, Z.; Liu, Z.
Electrochemical sensor based on a three dimensional nanostructured
MoS2 nanosphere-PANI/reduced graphene oxide composite for
simultaneous detection of ascorbic acid, dopamine, and uric acid.
RSC Adv. 2019, 9 (6), 2997−3003.
(40) Nagles, E.; García-Beltrán, O.; Calderón, J. A. Evaluation of the
usefulness of a novel electrochemical sensor in detecting uric acid and
dopamine in the presence of ascorbic acid using a screen-printed
carbon electrode modified with single walled carbon nanotubes and
ionic liquids. Electrochim. Acta 2017, 258, 512−523.
(41) Wu, D.; Li, Y.; Zhang, Y.; Wang, P.; Wei, Q.; Du, B. Sensitive
Electrochemical Sensor for Simultaneous Determination of Dop-
amine, Ascorbic Acid, and Uric Acid Enhanced by Amino-group
Functionalized Mesoporous Fe3O4@Graphene Sheets. Electrochim.
Acta 2014, 116, 244−249.
(42) Belaidi, F. S.; Civélas, A.; Castagnola, V.; Tsopela, A.; Mazenq,
L.; Gros, P.; Launay, J.; Temple-Boyer, P. PEDOT-modified
integrated microelectrodes for the detection of ascorbic acid,
dopamine and uric acid. Sens. Actuators, B 2015, 214, 1−9.
(43) Xu, G.; Jarjes, Z. A.; Desprez, V.; Kilmartin, P. A.; Travas-
Sejdic, J. Sensitive, selective, disposable electrochemical dopamine
sensor based on PEDOT-modified laser scribed graphene. Biosens.
Bioelectron. 2018, 107, 184−191.
(44) Anithaa, A. C.; Lavanya, N.; Asokan, K.; Sekar, C. WO3
nanoparticles based direct electrochemical dopamine sensor in the
presence of ascorbic acid. Electrochim. Acta 2015, 167, 294−302.
(45) Zhao, P.; Chen, C.; Ni, M.; Peng, L.; Li, C.; Xie, Y.; Fei, J.
Electrochemical dopamine sensor based on the use of a
thermosensitive polymer and an nanocomposite prepared from
multiwalled carbon nanotubes and graphene oxide. Microchim. Acta
2019, 186 (3), 134.
(46) Qian, T.; Yu, C.; Zhou, X.; Ma, P.; Wu, S.; Xu, L.; Shen, J.
Ultrasensitive dopamine sensor based on novel molecularly imprinted
polypyrrole coated carbon nanotubes. Biosens. Bioelectron. 2014, 58,
237−241.
(47) Ni, J.-A.; Ju, H.-X.; Chen, H.-Y.; Leech, D. Amperometric
determination of epinephrine with an osmium complex and Nafion
double-layer membrane modified electrode. Anal. Chim. Acta 1999,
378 (1), 151−157.
(48) Yuan, D.; Chen, S.; Hu, F.; Wang, C.; Yuan, R. Non-enzymatic
amperometric sensor of catechol and hydroquinone using Pt-Au-
organosilica@chitosan composites modified electrode. Sens. Actuators,
B 2012, 168, 193−199.
(49) He, J.; Qiu, R.; Li, W.; Xing, S.; Song, Z.; Li, Q.; Zhang, S. A
voltammetric sensor based on eosin Y film modified glassy carbon
electrode for simultaneous determination of hydroquinone and
catechol. Anal. Methods 2014, 6 (16), 6494−6503.

7318 DOI: 10.1021/acsanm.9b01794

ACS Appl. Nano Mater. 2019, 2, 7311−7318