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DOI 10.1007/s00604-015-1609-2
REVIEW ARTICLE
Abstract This review (with 110 refs.) gives an overview on the Introduction
progress that has been made in the past few years on the use of
gold nanoparticles (AuNPs) for use in sensors and analytical Neurotransmitters are important for a large array of functions
tools for the determination of dopamine (DA). Both AuNPs in both the central and the peripheral nervous systems as it
and their composites with other organic and inorganic materials delivers the message in the form of a nerve impulse from the
including noble metals are treated. Following an overview on the brain. DA can be produced only in a few, very specific regions
clinical significance of DA, we discuss the various analytical of the brain such as at the substantia nigra and the ventral
methods that are (a) electrochemiluminescence (ECL); (b) sur- tegmental area. An abnormal DA level in the brain cause
face enhanced Raman scattering (SERS); (c) colorimetric prob- several disease conditions, such as pleasurable, rewarding
ing and visual detection; and (d) the large class of electrochem- feelings, and sometimes even euphoria. Depression, stress,
ical sensors. Subsections cover sensors based on plain AuNPs, mental exhaustion, fatigue, low sex drive and low motivation
bimetallic NPs, AuNP-metal@metal oxide nanocomposites, are some of the symptoms of low DA level in human body. A
AuNP nanocomposites with organic polymers, AuNP nanocom- deficiency of DA in motor area of the brain may lead to mus-
posites with carbon nanotubes or with graphene, and finally sen- cle rigidity commonly known as Parkinsons disease which
sors based on ternary materials containing AuNPs. The review involves uncontrollable muscle tremor. The neurological dis-
ends with a conclusion on current challenges of sensors for DA orders such as schizophrenia and social anxiety or social pho-
and an outlook on future trends. bia associated with the presence of excessive amounts of DA
in human body [1]. Besides that, the disorder of DA in the
prefrontal cortex and frontal lobes of the brain contribute to
Keywords Dopamine . Gold Nanoparticles . attention deficit disorder and decline in neurocognitive func-
Electrochemistry . Electrochemiluminescence . Colorimetry . tions, especially memory, attention, and problem-solving, re-
Surface enhanced Raman scattering spectively. The development of a sensor for the precise and
selective measurement of DA in the presence of potential bio-
* Alagarsamy Pandikumar molecules interference at the abnormal levels characteristic of
pandikumarinbox@gmail.com living systems can make a great contribution to disease
* Nay Ming Huang diagnosis.
huangnayming@um.edu.my Although many sensor materials reported showed good
potential in detecting neurotransmitters [2], this review will
1
Low Dimensional Materials Research Centre, Department of
emphasize on AuNPs and their hybrids with bimetallic,
Physics, Faculty of Science, University of Malaya, 50603 Kuala metal/metal oxide, polymer, carbon nanotubes (CNT), and
Lumpur, Malaysia graphene. These AuNPs-based composites are used as the
2
Centre for Photoelectrochemistry, School of Chemistry, Madurai main material for detecting DA in various detection tech-
Kamaraj University, Madurai 625021, India niques. AuNPs have recently drawn an increasing attention
3
Department of Chemistry, Faculty of Science, Universiti Putra of many researchers in the field of sensors especially biosen-
Malaysia, 43400 UPM Serdang, Selangor, Malaysia sor attributed to its novel chemical, optical and physical
N. Yusoff et al.
Electrochemiluminescence (ECL)
Earlier reports show that the ECL assays has been proven to
be one of the powerful device which been used for the sensi-
tive detection of a wide variety of analytes including DA [12].
Basically there are three system of ECL that extensively used
Fig. 1 Some of the properties owned by AuNPs for the detection of DA that are; (1) tris(2,2-bipyridyl)
Gold nanoparticle based sensor platform for dopamine
ruthenium(II) (Ru(bpy)3 2+) [13] (2) quantum dots (QDs) [14], The recovery of ECL signal by spiked analyte in human urine
(3) peroxydisulfate systems [15]. Although Ru(bpy)32+-based and serum samples ranged from 94 to 106 % attesting the
ECL assays had extensively used for detection of DA, how- validity of the developed method.
ever, it need a high-cost to produced due to the consumption Interestingly, label-free ECL assays have been developed
of the expensive reagent and extra pump to deliver the reagent using AuNPs as the luminophores in ECL systems due to its
to the electrochemical cell continuously. Moreover, simplicity, time-saving, and low-cost. AuNPs has been fre-
Ru(bpy)32+ can only be use once per reaction because it is quently used as the luminophores due to their unique features
easily polluted with the analytes from the solution. Besides including size-dependent optical, electronic, and electrochem-
that, QDs-based ECL assays is also not a practical method as ical properties as well as ease of synthesis, surface function-
QDs such as cadmium telluride (CdTe) and cadmium sulphide alities and low toxicity. Li and co-workers reported the fabri-
(CdS) are not stable enough over time, has inherent toxicity cation of DA sensor by ECL technique using the bovine serum
and lower ECL signals. In addition, it requires a high negative albumin (BSA)-stabilized Au nanoclusters (AuNCs) modified
potential in order to produce ECL. This condition leads to ITO electrode [17]. The results show that the AuNCs are a
some unforeseen reaction which makes it unfavorable to its promising material for ECL investigations as the ECL signal
application. In the case of peroxydisulfate-based ECL assays, of the AuNCs modified ITO electrode is about 5 times higher
this type of sensor suffers from the weak ECL emission which than that of bare ITO. This AuNCs/ITO-based ECL assays
was not adequate for sensitive analytical application. Due to also showed an acceptable selectivity and sensitivity for DA
these drawbacks, the applications of the above three kinds of detection with a linear range of 2.5 to 47.5 M. The assembly
ECL systems in bioassay is limited. of AuNCs is facilitated by the presence of BSA layer on its
Recent trend in the development of probes for biomole- surrounding. The new combined materials provided abundant
cules ECL assays has been reported on the use of functionalities such as carboxyl and amino groups that facili-
n a n o m a t e r i a l s e s p e c i a l ly A u N P s to a m p l i f y t h e tate the immobilization of AuNCs onto hydroxylated indium
peroxydisulfate ECL intensity for biomolecules detection. tin oxide (ITO) electrodes and in the same time stabilized the
For example, Yan and co-workers have used the reduced AuNCs. They reported the enhancement of ECL signal when
graphene oxide (RGO) to incorporate with AuNPs in order DA is injected into the electrolyte solution due to the forma-
to amplify the ECL signal for the development of sensitive tion of a charge transfer complex between DA and ITO, which
and selective peroxydisulfate ECL assays specifically for DA accelerate the electron injection into the conduction-band of
determination [15]. Due to the synergistic amplification of ITO. The electron will then be transferred to the LUMO of
AuNPs and RGO, the ECL intensity of peroxydisulfate solu- AuNCs which then generates the Au25* with the emission of
tion was increased and the onset potential also decreased. The light upon reacting with SO 4 radicals produced by
ECL intensity was further enhanced upon injecting DA into electroreduction of S2O82 coreactant. The possible ECL
the electrolyte which indicates that the presence of DA facil- mechanism is as follows [17]:
itates the electrochemical reduction of S2O82 hence an ECL
IT O
assays for DA detection can be constructed. The development Au25 Au
25 1
of ECL DA assays demonstrated a wide linear response of
S 2 O2 e S 2 O2 2
0.0240 M with a detection limit of 6.7 nM (S/N=3). The 8 8
gold nanoclusters/indium tin oxide; AuNPRGO/GCE = Gold nanoparticles-reduced graphene oxide/glassy carbon electrode; AuNF@g-C3N4PANI/GCE = gold nanoflower@graphitic carbon nitride
Ref.
rGO/MWCNTs/AuNPs/GCE = reduced graphene oxide/multiwall carbon nanotubes/gold nanoparticles/glassy carbon electrode; BSA-stabilized Au nanoclusters/ITO = bovine serum albumin-stabilized
[16]
[17]
[15]
[18]
and simple as it requires minimum sample preparation, high
sensitivity. The SERS technique uses the idea that the mol-
Dopamine hydrochloride
Dopamine hydrochloride
scattering closely related to the vibrational and rotational
modes excited in the molecules. These molecules when ir-
radiated with different frequencies light generate a specific
Human plasma
Real sample
injection
urine as a fingerprint for detecting and identifying specific sub-
stances. The plasmon phenomenon will be generated on the
metal surface induced by laser light and this phenomenon
UA, AA, epinephrine, norepinephrine,
0.0240 M
Linear range
0.270 M
detection can be divided into two which are direct and indi-
detection
Limit of
6.7 nM
1.7 nM
0 to 1.6 V
AuNF@g-C3N4PANI/
Au NPsRGO/GCE
nanoclusters/ITO
BSA-stabilized Au
Material
Table 1
GCE
AuNPs/Dopamine = gold nanoparticles/dopamine; AgcoreAushell = silver-gold nanoparticles; CGN-Dopamine = Chitosan-Gold Nanoshell-dopamine; Flower-like Au/ITO = flower-like gold nanostructure/
Ref.
[20]
[22]
[23]
[24]
[25]
the longitudinal SPR band of AuNPs is very sensitive to
changes in the local environment, including solvent, substrate,
icantly reduced.
Linear range
1 10 mM
1 10 mM
NA
NA
NA
1382 cm1
1348 cm1
Material Preparation method Response peak Limit of detection Linear range Interferences Real sample Ref.
Fe3O4-DA-DTSSP- Trisodium citrate reduction 520 nm 10 nM dihydroxyphenylacetic acid, glutamic acid, [31]
AuNPs method norepinephrine, tyrosine
DAmelamineAuNPs Citrate-mediated reduction 530 nm 30 nM 300 nM - 10 mM Tyramine, phenethylamine Urine [29]
of HAuCl4
GNPs induced by Cu2+ Stirring 525 & 650 nm 200 nM 500 nM 10 M UA, AA, -amino acids, glutathione, Human serum [33]
glucose,
DSP-AuNPs induced by Trisodium citrate reduction 520 & 650 nm 2 nM UA, AA, dihydroxyphenyl acetic acid, artificial cerebrospinal [30]
Fe3+ method epinephrine, glutamic acid, norepinephrine, fluid (aCSF)
tyrosine, catechol, epinephrine,
AuNPs induced by Cu2+ Citrate reduction method 520 & 670 nm 30 nM 3.3108 - 1.0107 UA, AA, serotonin, Mg2+, Ba2+, Ca2+, Al3+, [26]
Ni2+, Ag+, Hg2+, Pb2+, Cu2+
DMAPAuNPs Core-etching process 415 & 520 nm 5 nM 10105 n AA, homovanillic acid, catechol, glutathione [34]
AHMT-AuNPs Citrate-mediated reduction 520 & 650 nm 70 nM 0.21.1 M histidine, tyrosine, tryptophan, phenylalanine, Human serum & urine [35]
lysine, catechol, glutamic acid, acrobatic acid,
glucose, fructose, glutathione, 2,3,4-
trihydroxybenzoic acid, gallic acid, ferulic acid,
UA, urea, histamine, serotonin, catechol,
epinephrine, isoprenaline, norepinephrine
AuNRsAg+ Silver ion-assisted seed 524 & 620 nm 47 nM 0.212 M K+, Na+, Ca2+, Cl, AA, citric acid, cysteine, Human serum [32]
mediated method aspartic acid, glutamic acid, lysine, glucose
AuNPs Salt-induced aggregation 524 & 660 nm 360 nM 0.545.4 M 3,4- dihydroxyphenylalanine, catechol, epinephrine, [36]
3,4-dihydroxyphenylacetic acid, homovanillic
acid, AA
AuNPs induced by MA Citrate-mediated 530 nm 33 nM 33 nM 3.33 mM adrenaline, tyramine and phenethylamine Human serum [37]
reduction in human serum
Fe3O4-DA-DTSSP-AuNPs = iron oxide-dopamine- dithiobis(sulfosuccinimidylpropionate)-gold nanoparticles; GNPs = gold nanoparticles; DSP-AuNPs = dithiobis(succinimidylpropionate)-gold nano-
particles; DMAPAuNPs = 4-(dimethylamino) pyridine-gold nanoparticles; AHMT-AuNPs = 4-amino-3-hydrazino-5-mercapto-1,2,4-triazol- gold nanoparticles; AuNRsAg+ = gold nanorods-silver
ions; AuNPs induced by MA = gold nanoparticles induced by melamine
N. Yusoff et al.
Gold nanoparticle based sensor platform for dopamine
0.56 M with a detection limit of 7.8 nM (S/N=3) which has linear range of 1 nM to 5104 M was achieved with
been achieved after the oxidation of DA at the modified elec- an increase in their oxidation peak currents and lower in
trode. Moreover, it also exhibits a recoveries in a range be- their oxidation peak potentials. The result attributed to
tween 96.7 and 104.9 % with RSD < 4.1 % after been the ability of AuNPs/ITO electrode to accelerate the rate of
employed for detecting DA in human serums. electron transfer thus increase the electrocatalytic activity.
Besides using AuNPs modified Au/GC electrode, AuNPs AuNPs modified ITO electrode have also been used by
modified indium tin oxide (ITO) electrode also have been Aldana-Gonzlez and co-workers who have developed a sim-
widely used for the fabrication of electrochemical DA assays. ple method for the modification of ITO electrode with AuNPs
This type of electrode contributes prominent characteristics [44]. This AuNPs/ITO electrode was employed for the direct
such as optically transparent and possesses high conductivity electrochemical detection of DA which was carried out by
with low background current. Goyal et al. described an means of DPV. The electrode perform a detection limit of
electrochemical biosensor using AuNPs decorated ITO 34.5 M (S/N=3) and a linear range of 10 to 900 M in the
platforms for highly sensitive detection of DA in DA presence of AA and UA. Table 4 shows the analytical param-
hydrochloride injection, human serum and urine [43]. eters reported for different AuNPs modified electrodes to-
A lower detection limit of 0.5 nM (S/N=3) and wide wards DA quantification.
Material Preparation method Detection Working Limit of Linear Interferences Real sample Ref.
method potential detection range
Au/ATP/ABA (SAM)/GCE Self-assembly of AuNPs on DPV 0.42 V 9.2 M 15135 M AA DA hydrochloride injection [45]
sulfhydryl-terminated monolayer (vs. Ag/AgCl)
Cyst(SAM)/nano-Au Nano-Au self-assembly SWV 0.2 V 0.22 M NA AA [40]
(vs. Ag/AgCl)
nano-Au/CA/GCE Self-assembly of AuNPs on DPV 0.175 V 4 nM 10 nM-25 M AA DA hydrochloride injection [46]
cysteamine film (vs. SCE)
GNP/Ch/GCE Electrodeposition DPV 0.23 V 0.12 M 0.280 M AA, UA DA hydrochloride injection [47]
(vs. SCE)
Pectin-AuNP/GCE Electrodeposition CA 0.2 V 6.1 nM 20900 nM AA, UA, arterenol, histidine, DA hydrochloride injection [48]
(vs. Ag/AgCl) tyrosine
GNs/HDT/OT (SAM)/Au Self-assembly of AuNPs DPV 0.53 V 90 M 0.21.2 mM AA [49]
(vs. SCE)
Au-DT/MOA(SAM)/Au Self-assembled monolayer CA 0.15 V 20 nM 0.015 M UA Urine [50]
(vs. Ag/AgCl)
SiO2/MPTS/Au Solgel method SWV 0.494 0.438 M 0.220 M AA, UA [51]
(vs. SCE)
GS/Au25/GCE Solgel method CV 0.34 V 0.3 M 0.53249.2 M AA [52]
(vs. Ag/AgCl)
ITO/AuNPs Immersion method (in poly-L- DPV 0.78 V 34.5 M 10900 M AA, UA [44]
Lysine solution) (vs. Ag/AgCl)
Au/ITO Seed-mediated method SWV 0.22 V 0.5 nM 1 nM- 500 M AA, serotonin DA hydrochloride injection, [43]
(vs. Ag/AgCl) Human serum & Urine
Aunanofilm/Au The oxidization at a high potential DPV 0.22 V 1.5 M 1.527.5 M AA [53]
and the reduction by glucose (vs. SCE)
AuNPs/MIES Electropolymerization method in the CA 0.16 V 7.8 nM 0.020.56 M AA, UA Human serum [42]
presence of DA and p- (vs. SCE)
aminobenzenethiol (p-ATP)
DAR/Au-Si Electrodeposition from sulfite-based DPV 0.2 V 1 M 112 M AA [54]
Au(I) electrolytes (vs. Ag/AgCl)
GNR/GCE Anodic aluminum oxide template SWV 0.15 V 5.5 nM 10100 nM AA [55]
technique (vs. SCE)
NPG/GCE Selective dissolution (dealloying) DPV 0.25 V 17 nM 0.21 M AA [56]
of Ag from Ag/Au alloys (vs. SCE)
NPGF/Au Multicyclic electrochemical SWV 0.15 V 1 nM NA AA [57]
alloying/dealloying (vs. SCE)
AuNW/PET Direct current electrochemical CA 0.2 V 26 nM 0.2600 M AA, UA, citric acid [8]
depositions (vs. Ag/AgCl)
Pt/Au/GCE Electrochemical deposition DPV 0.35 V NA 0.0240.384 mM AA, UA DA hydrochloride injection [49]
(vs. Ag/AgCl)
Pd/Au/GCE Electrochemical fabrication DPV 0.15 V NA 0.56.95 M UA, epinephrine [50]
(Ionic liquid assisted) (vs. Ag/AgCl)
N. Yusoff et al.
Gold nanoparticle based sensor platform for dopamine
tionalized silica/Gold nanoparticles electrode; GS/Au25/GCE = Glutathione/Gold nanoparticles/Glassy carbon electrode; ITO/AuNPs = Indium tin oxide/Gold nanoparticles; Au/ITO = Gold nanoparticles/
Indium tin oxide; Aunanofilm/Au = Gold nanofilm/Gold electrode; AuNPs/MIES = Gold nanoparticles/Molecularly imprinted polymers electrode; DAR/Au-Si = Dendritic gold rod/Silicon wafer; GNR/
monolayer)/Gold electrode; Au-DT/MOA(SAM)/Au; Gold nanodendrite/8-mercaptooctanoic acid (self-assembled monolayer)/Gold electrode; SiO2/MPTS/Au/CPE = 3 - mercaptopropyl - thiol func-
GCE = Gold nanorods/Glassy carbon electrode; NPG/GCE = Nanoporous gold/Glassy carbon electrode; NPGF/Au = Nanoporous gold film/Gold electrode; AuNW/PET = Gold nanowires/ polyethylene
Ref.
er)/Gold nanoparticles electrode; nano-Au/CA(SAM)/GCE = Gold nanoparticles/Cysteamine (self assembles monolayer)/Glassy carbon electrode; GNP/Ch/GCE = Gold nanoparticles/Choline/Glassy
Au/ATP/ABA(SAM)/GCE = Gold nanoparticles/aminothiophenol/Aminobenzoic acid (self-assembled monolayer)/Glassy carbon electrode; Cyst(SAM)/nano-Au = Cystamine (self-assembled monolay-
carbon electrode; Pectin-AuNP/GCE = Pectin-stabilized gold nanoparticle/Glassy carbon electrode; GNs/HDT/OT(SAM)/Au = Gold nanoparticles/1,6-Hexanedithiol/1-octanethiol (self-assembled
[58]
[59]
Electrochemical sensors using bimetallic nanoparticles
DA hydrochloride
to forming bimetallic nanoparticles especially in its catalytic,
optical and electrical properties [60, 61]. In 2007, Thiagarajan
Real sample
0.12 M
Limit of
0.2 M
(vs. Ag/AgCl)
0.16 V
DPV
Electrodeposition
nanostructure/Au
GCE
chemical properties. Mahshid et al. [64] have developed a DA Electrochemical sensors using AuNP nanocomposites
assays using an electrode modified with TiO2 nanotubes and with organic polymers
electrodeposited Pt, Pd and gold NPs. The current response of
AuNPs/Pt/Pd/TiO2 modified electrode recorded by DPV Conducting polymers which also known as intrinsically
shows an increment upon addition of DA and exhibits a limit conducting polymers (ICPs) are an organic polymer that pos-
of detection of 3 108 M (S/N = 3) and a sensitivity of sesses a high electron affinity and high electronic conductivity
4.57 A M1. The constructed assays was then used for by several orders of magnitude of doping. These associated to
the detection of DA in real sample analysis using human urine the -electron backbone owned by ICPs. The ease of synthe-
samples and the results shows that the modified electrode able sis of ICPs and theirs unique properties encourages re-
to achieve recovery up to 112.6 %. searchers to employ this material in the fabrication of biosen-
Due to the excellent properties owned by molybdenum sors. Some of the ICPs groups that are frequently used in
disulfide (MoS2), Sun and co-workers has constructed biosen- biosensors application are polyacetylene [81], polythiophene
sor for DA based on AuNPs/MoS2 film modified electrode in [82 ], p oly(p -ph eny lene viny le ne) [ 83 ], poly(3,4-
order to improve their sensing performance towards DA ethylenedioxythiophene) [84], polypyrrole [85], and
(Fig. 8) [68]. The AuNPs/MoS2 film modified electrode polyaniline [86] where their structures are shown in Fig. 9.
showed excellent electrocatalytic activity toward the oxidation Due to the superb quenching ability of AuNPs to form
of AA, DA and UA with three well-resolved oxidation peaks nanocomposites with ICPs, an electrochemical DA assays
at 0.046 V, 0.105 V and 0.242 V (vs. SCE). The excellent based on AuNPs/polymer modified electrode has been devel-
electrocatalytic activity of MoS2 for oxidation of DA attributed to oped. Recently, the surface modification of conventional elec-
the ultra-small nanoparticles which expose a large fraction of trodes with AuNP/polymer nanocomposites provides new and
edge site and high surface area which increased surface active interesting properties in the construction of DA assays. The
site density for enzyme immobilization. The DPV was carried development of AuNP/polymer nanocomposites modified
out for simultaneous determination of AA, DA and UA. The glassy carbon (GC) electrode started in 2004 when Kumar
result reveal that the peak currents of these ternary mixture were et al. explore the synergic effect between a polymer matrix
linear with the concentrations in the ranges from 1 to 70 mM, 50 and AuNPs for selective determination of DA [70]. In the
nM-4 mM and 107 mM with detection limit of 100 mM, 50 nM study of AuNPs incorporated PEDOT film modified GC elec-
and 10 mM, respectively (S/N=3). The comparison of the sens- trode, they observed that AuNPs whose been surrounded by a
ing characteristics of DA sensors with various AuNPs/metal ox- hydrophobic sheath tend to reside within these hydrophobic
ide modified electrodes is presented in Table 5. regions of PEDOT. This interaction forms a strong synergic
Gold nanoparticle based sensor platform for dopamine
Fig. 8 DPV profiles at AuNPs@MoS2/GCE in 0.1 M PB solution 30 mM, and (C) containing 50 mM AA, 4 mM DA and different concen-
(pH 7.0) (A) containing 6 mM DA, 30 mM UA and different concentra- trations of UA from 0.05 mM to 50 mM. (DF) The plots of the oxidative
tions of AA from 0.05 mM to 100 mM, (B) containing 12 mM AA, peak currents versus the concentrations of AA, DA and UA [68]
10 mM UA and different concentrations of DA from 0.05 mM to
effect between both materials. At one point, the effect will extensively used as a platform to growth AuNPs/PEDOT
increase the DA oxidation current thus enhanced the sensitiv- films for the detection of DA. Liu et al. loaded AuNPs and
ity of the assyas where it showed a sensitivity of 0.85 A PEDOT on a Pt disk electrode using electropolymerization
nM1 with a detection limit of 2 nM (S/N=3) for DA deter- technique to construct a DA assays [87]. The electrode exhib-
mination. Besides using GC electrode, Pt disk electrode also ited a wide linear response to DA from 6 M to 0.013 M with a
Table 5 Summary on the performance of various Au@metal oxide modified electrodes towards DA detection
Material Preparation method Detection Working Limit of Linear Interferences Real sample Ref.
method potential detection range
Au/Pt/Pd/TiO2 NTs = Gold nanoparticles/Platinum/Palladium/Titanium dioxide nanotubes electrode; AuNPs/SiO2/MIPs = Gold nanoparticles/Silicon
dioxide/Molecularly imprinted polymers; CeO2/Au/GCE = Cerium oxide/Gold nanoparticles/Glassy carbon electrode; Fe3O4/Au/PVS/ITO = Iron
oxide/Gold nanoparticles/Poly(vinyl sulfonic acid)/Indium tin oxide; AuNPs/MoS2/GCE = Gold nanoparticles/Molybdenum disulfide/Glassy carbon
electrode; Au/ZnO/GCE = Gold nanoparticles/Zinc oxide/Glassy carbon electrode
N. Yusoff et al.
detection limit of 0.2 M (S/N=3) and showed a good stability to the synergic influence provided by the combined presence
of about 8 months. They discovered that the stable chemical and of PAT and AuNPs. The applicability of PAT/AuNPs modified
physical characteristics owned by PEDOT lead to the good long- electrode for the selective and sensitive determination of DA
term stability and high sensitivity of the electrode. in the real samples has been proven as they showed 96 to
Poly(4-aminothiophenol) (PAT) is another polymer used to 101 % of recovery when being tested in human blood serum.
entrap AuNPs in order to improve the analytical performance The comparison of analytical parameters for the determination
of electrodes. Figure 10 display the fabrication of PAT/AuNPs of DA at different AuNP/polymer nanocomposites modified
modified electrode through a cyclic electrochemical process electrode has shown in Table 6.
reported by Gopalan [72]. AuNPs was distributed on the PAT
matrix over the surface of GC electrode by cyclic electro- Electrochemical sensors using AuNP nanocomposites
chemical process and a linear response range from 10 to with carbon nanotubes
50 M of DA concentration with the sensitivity of
0.22 A M1 was achieved in the presence of AA. This CNTs possess high electric conductivity for the electron trans-
electrode was also able to separate the voltammetry signal fer reactions with better electrochemical and chemical stabil-
between AA, DA and UA in the interference study recorded ities in both aqueous and non-aqueous solutions which make
by DPV. They found that the simultaneous oxidation of AA it suitable for the modification of various electrode compared
and DA shows a wider potential difference (Ea 325 mV) due to other carbon materials. In 2009, Ragupathy and co-workers
Fig. 10 Fabrication of PAT-AuNPs modified electrode through a cyclic electrochemical process [72]
Table 6 Comparison of analytical performance of different AuNPs/polymers nanocomposites modified electrodes in the detection of DA
Material Preparation method Detection Working Limit of Linear Interferences Real sample Ref.
method potential detection range
injection
nano-Au/PPyox/GCE Electrodeposition technique DPV 0.2 V 15 nM 75 nM- 20 M Serotonin Human blood serum [73]
(vs. SCE)
Au/PEDOT/GCE Self-assembly of thiophene DPV 0.1 V NA 2080 M AA, UA [74]
rings on gold surfaces (vs. Ag/AgCl)
AuNPs/P3MT/GCE Electrodeposition technique DPV 0.19 V 2.4107 135 M AA, UA DA hydrochloride [75]
(vs. SCE) injection & urine
GNPs/PANI/GCE Electrodeposition technique CA 0.6 V 0.8 M 3115 M DA hydrochloride [76]
(vs. SCE) injection
AuNPs/PANI/CS/GCE One-step chemical oxidative DPV 0.264 V 5 M 101700 M AA Human serum [77]
polymerization (vs. SCE)
PEDOT/Aunano/Au Electrodeposition technique LSV 0.493 V 0.39 nM 0.520 M AA, acetaminophen Urine [78]
(vs. Ag/AgCl) (paracetamol)
Au-NPs/PANI/BDD Electrochemical deposition SWV 0.27 V 0.03 M 0.15500 M AA [79]
method (vs. Ag/AgCl)
nanoAu/PMT/GCE Electrodeposition technique DPV 0.23 V 37 nM 50 nM-1 M UA [80]
(vs. SCE)
nanoAus/PEDOT/Pt Electropolymerizing CA 0.35 V 0.2 M 6.0 M-13 mM. Human serum [65]
PEDOT in ionic liquid, (vs. SCE)
electrodeposition
technique
Au/PEDOT/GCE = Gold nanoparticles/ poly (3,4-ethylenedioxythiophene)/Glassy carbon electrode; Au/PANI/GCE = Gold nanoparticles/Polyaniline/Glassy carbon electrode; PAT/Aunano/GCE = Poly(4-
aminothiophenol)/Gold nanoparticles/Glassy carbon electrode; nano-Au/PPyox/GCE = Gold nanoclusters/Overoxidized-polypyrrole/Glassy carbon electrode; AuNPs/P3MT/GCE = Gold nanoparticles/
poly(3-methylthiophene)/Glassy carbon electrode; GNPs/PANI/GCE = Gold nanoparticles/Polyaniline/Glassy carbon electrode; AuNPs/PANI/CS/GCE = Gold nanoparticles/Polyaniline/Chitosan/Glassy
carbon electrode; PEDOT/Aunano/Au = Poly(3,4-ethylene-dioxythiophene)/Gold nanoparticles/Gold electrode; Au-NPs/PANI/BDD = Gold nanoparticles/Overoxidized polyaniline/Boron-doped diamond
electrode; nanoAu/PMT/GCE = Gold nanoparticles/ poly(Lmethionine)/Glassy carbon electrode; nanoAus/PEDOT/Pt = Gold nanoparticles/Poly (3,4-ethylenedioxythiophene)/Platinum electrode
N. Yusoff et al.
has fabricated a sensor incorporating AuNPs with multi- behaviour of DA which recorded by differential pulse anodic
walled carbon nanotubes (MWCNTs) which was grafted onto stripping voltammetry (DPASV). A low limit of detection of
silica network via solgel process [88]. The MWCNTs/ 0.04 M (S/N=3) with a linear range of 0.06 to 8 M was
AuNPs modified electrode was employed for determination achieved and this modified electrode also shows the capability
of DA in the presence of AA evaluated by DPV. The results to effectively avoid the interference of AA and UA (Fig. 11).
revealed that the modified electrode can electrochemically The combination of AuNPs and MWCNTs forming a new
discriminate the sensing of AA and DA with a wide potential hybrid material which proven helps to facilitate electron trans-
separation (Epa~0.26 V). Hence, it shows the possibility for fer between the electrically active material and the electrode
simultaneous independent measurement of DA and AA at this surface, thus enhance the sensitivity of the sensor.
MWCNTs/AuNPs modified electrode. This promising anti- A novel nanocomposite promising for the development of
interference capability to AA and DA results from the syner- effective electrochemical biosensors for the detection of DA
getic effect of combining AuNPs and MWCNTs grafted onto was successfully synthesized by A. Curulli and co-workers
silica network. In addition, the synergetic effect also enhanc- [90]. By taking the advantage of SWCNTs that could mediate
ing the catalytic activity. In an interesting work by Yang et al., fast electron-transfer kinetics for a wide range of electroactive
they developed a modified GC electrode system by casting a species and excellent catalytic properties possessed by
dispersed solution of AuNPs/MWCNTs nanocomposites in AuNPs, they have developed a SWCNTs/AuNPs modified
Nafion on GC electrode [91]. In this work, the modified elec- GC electrode for electrochemical sensing study. The electro-
trode was employed to investigate the electrochemical chemical signal of oxidation of DA at SWCNTs/AuNPs
Fig. 11 (A) SEM images of Au/MWNTs nanocomposite. In 0.1 M phos- DA: 0.8 M DA (a), 0.8 M DA+0.4 mM AA+0.4 mM UA (b) and
phate buffer solution (pH 6.0), (B) DPASV for different concentrations of 0.4 mM AA (c); (D) CVs for 60 M DA at Au/MWNTs/Nafion/GCE (a),
DA at Au/MWNTs/Nafion/GCE (ai): 8, 6, 4, 2, 0.8, 0.6, 0.4, 0.2, MWNTs/Nafion/GCE (b), GCE (c), Nafion/GCE (d) and Au/MWNTs/
0 M, inset: the calibration curve for the determination of DA; (C) the Nafion/GCE without DA (e), scan rate: 80 mV s1 [91]
effect of 0.4 mM AA and 0.4 mM UA on the DPASV response of 0.8 M
Gold nanoparticle based sensor platform for dopamine
modified electrode undergoes amplification compared to the The applicability of this modified electrode in real sample
conventional GC electrode indicating higher sensitivity to- analysis was also been studied. For this purpose, DA concen-
wards DA detection. The nanocomposite might provide tration was determined in DA hydrochloride injection which
higher electron conduction pathways due to a synergistic ef- serves as a real sample where the recovery is found to be in the
fect between AuNPs and SWCNTs leading to the higher cat- range of 96102 %. Thus, the achievement of excellent recov-
alytic properties. The analytical parameters reported for dif- eries of DA validates that this nanocomposite materials remain
ferent Au-CNTs modified electrodes towards DA quantifica- promising for real sample analysis and in the same time pro-
tion are shown in Table 7. vide a new platform for designing effective assays.
Besides using AuNPs, there are also studies that use the
Electrochemical sensors using AuNP nanocomposites gold nanoplates to produce nanocomposite together with
with graphene graphene as reported by Wang et al. [98]. Electrochemically
reduced graphene oxide and gold nanoplates were deposited
Electrochemical DA assays based on AuNP/graphene nano- on the surface of GC electrode before being applied to the
composites are also extensively studied starting from 2012. simultaneous determination of AA, DA, and UA. The as-
Tian and co-workers successfully fabricate an AuNPs/-cy- fabricated Au/RGO/GC modified electrode exhibits excellent
clodextrin/graphene (AuNPs/-CD/Gra) modified GC elec- analytical performance for the simultaneous detection of DA,
trode for simultaneous determination of AA, DA and UA AA and UA, with a detection limit of 1.4 M, 51 M, 1.8 M
[92]. -CD is used as a dispersant and stabilizer for HAuCl4 (S/N=3) and a linear range of 6.841 M, 0.241.5 mM and
and it also acts as a reducing agent for GO and AuCl4 in order 8.853 M, respectively. The high selectivity and sensitivity
to form graphene and AuNPs, respectively. This modified for individual and simultaneous determination of AA, DA,
electrode exhibit excellent sensing behaviour towards simul- and UA with low detection limits and wide linear ranges at-
taneous detection of AA, DA and UA with linear responses in tributed to the large surface area and unique conductivity of
the ranges of 302000, 0.5150 and 0.560 M, respectively RGO and the excellent electrocatalytic activity of AuNPs. The
and the low detection limit of 10, 0.15, and 0.21 M, respec- detection of DA in the rat serum shows a recovery ranged
tively. The good stability, sensitivity and selectivity towards between 97.5 and 102 % indicate that the Au/RGO/GCE
DA shown by this modified electrode attributed to the increase could be used for the determination of AA, DA, and UA in
in electric conductivity and the effective surface area provided real samples. Table 8 shows the different types of Au-
by graphene. graphene-based DA sensor with their limit of detection and
Another work that used AuNPs/graphene modified elec- linear range.
trode for the detection of DA in the interference of AA and
UA is done by Zhu et al. [97]. A novel hollow AuNP/ Electrochemical sensors using ternary materials
graphene nanocomposite was synthesized using simple two- containing AuNPs
steps method before being deposited on the surface of GC
electrode using simple drop-casting method. The DA could In order to couple the properties owned by AuNPs with the
be detected in a linear range from 0.08 M to 600 M with a properties of other nanomaterials, AuNPs has been incorpo-
detection limit of 0.05 M (S/N=3) using amperometric tech- rated into nanocomposites. The catalytic activity properties of
nique. Based on the result of DPV, the modified electrode the new hybrid material are expected to enhance hence helps
effectively avoids the interference of AA and UA (Fig. 12). to increase the sensitivity and selectivity of a new sensor.
Table 7 Analytical parameters reported for different Au-CNTs modified electrodes towards DA quantification
Material Preparation method Detection Working Limit of Linear Interferences Real sample Ref.
method potential detection range
MWNT/silica-NW/AuNPs/GCE = Multiwalled carbon nanotubes/silica network/Gold nanoparticles/Glassy carbon electrode; Au/CNF/CPE = Gold
nanoparticles/Carbon nanofiber/Carbon paste electrode; SWCNTs/AuNp/GCE = Singlewalled carbon nanotubes/Gold nanoparticles/Glassy carbon
electrode; Au/MWNTs/GCE = Gold nanoparticles/Multiwalled carbon nanotubes/Glassy carbon electrode
N. Yusoff et al.
Table 8 Summary of performance of various Au-graphene nanocomposites modified electrodes towards DA detection
Material Preparation method Detection Working Limit of Linear Interferences Real sample Ref.
method potential detection range
AuNPs/ -CD/Gra/ In-situ thermal reduction SWV 0.426 V 0.15 M 0.50150 M AA, UA Human urine [92]
GCE of GO and HAuCl4 with (vs. SCE)
-cyclodextrin under alkaline
condition
AuNPs/rGO/GCE Electrostatic layer-by-layer DPV 0.116 V 0.02 M 160 M UA [93]
(LBL) self-assembly technique (vs. SCE)
AuNPs/rGOS/ITO Electrodeposition technique DPV 60 nM 101000 M AA, UA Beef sample [94]
AuNPs/GNS/GCE One-step solvothermal DPV 0.15 V NA AA, UA [95]
approach (vs. Ag/AgCl)
GE/Au/GE/CFE Layer-by-layer assembly DPV 0.1 V 0.59 0.5943.955 M NaCl, KCl, NaNO3, Urine [96]
(vs. SCE) AA, glucose, urea,
and NH4Cl
HAu/G/GCE Mixing an aqueous solution CA 0.4 V 0.05 0.08600 M AA, UA DA hydrochloride [97]
of HAu NPs with a poly (vs. SCE) injection
(N-vinylpyrrolidone)-
functionalized graphene
Au/RGO/GCE Electrochemical reduction, DPV 0.15 V 1.4 6.841 M AA, UA Rat serum [98]
electrodeposition method (vs. SCE)
AuNP/Graphene/ Chemical reduction, classical DPV 0.15 V 1.86 M 51000 M AA Human serum [99]
GCE citrate reduction method (vs. SCE)
Zhou and co-workers has developed a sensor for the detection (S/N3), respectively. The recovery determination of DA with
of DA based on Dawson-type phosphovanadotungstate Au/Pd/RGO/GC modified electrode shows a recovery ranged
K8P2W16V2O62 18H2O (P2W16V2) decorated by AuPd alloy between 97.1 to 102.5 %. Table 9 lists the comparison of the
nanoparticles (AuPd) using layer-by-layer self-assembly sensing characteristics of DA assays with ternary materials
method (Fig. 13). The (P2W16V2/Au/Pd/PEI)8 modified elec- (including AuNPs) modified electrodes reported in the
trode displays an excellent sensitivity and selectivity for DA literature.
over AA with a limit of detection of 0.217 M and 0.671 M
(S/N=3), respectively. The excellent sensing performance in-
cluding high sensitivity, good selectivity, higher stability and Conclusion and future outlooks
wide linear range shown by this modified electrode resulting
from the outstanding electrocatalytic behavior owned by this Gold nanostructures such as nanorods, nanoparticles,
new hybrid material. Results of the recovery tests obtained for nanodendrites, nanowires and nanoporous have been used ex-
determination of DA in blood serum sample exhibits a recov- tensively in various fields of applications especially in the
ery ranged between 100.13 to 100.5 %, indicating that the fabrication of novel sensors for the detection of biomolecules
modified electrode could be used for the determination of including neurotransmitter DA. Among all the gold nano-
AA, DA, and UA in commercial samples. structures, gold nanoparticles (AuNPs) have been widely used
Another interesting approach to improve the sensing per- for creation of DA assays because it offers the advantages of
formance is by incorporating bimetallic materials with unique physical, chemical, and mechanical properties. AuNPs
graphene. Taking advantages of the metal individual proper- which have small size with larger surface area provides a well-
ties, the addition of the second metal to form bimetallic mate- established platform for conjugation of biomolecules, thus
rials brings about variations in particle size, shape, surface making it the most effective material for fabricating DA as-
morphology, chemical and physical properties including cata- says. There is no doubt that AuNPs and AuNP-based nano-
lytic activity and chemical selectivity. In the work reported by composites have a good stability and strong electrocatalysis
Jiang et al. [110], they fabricate AuPd/RGO/GC modified properties which make it a promising material to develop oth-
electrode for simultaneous determination of DA, AA and er neurotransmitters sensors or bio-devices. In order to devel-
UA. Reduced graphene oxide (RGO) serve as a platform to op an excellent biosensor, several factors need to be given a
support catalytically active AuPd bimetallic nanoparticles dur- serious attention and a good understanding in term of the
ing heterogeneous catalytic reactions. The combination of properties of AuNPs, the interaction between AuNPs and an-
these ternary materials which deposited on the GC electrode alyte molecules and mechanisms of detection.
develops a sensor that has a high sensitivity and selectivity. This review on the potential of AuNPs in detecting DA by
The results for simultaneous detection of AA, DA, and UA, using various techniques may facilitate the development of
investigated by DPV demonstrated that this modified elec- high-performance but low-cost sensors. Optical sensor
trode have a linear response ranges of 1800, 0.1100, and (ECL, SERS and colorimetric) based on AuNPs and
0.1350 M with detection limits of 0.28, 0.024, and 0.02 M AuNPs-based nanocomposites provided a simple analytical
Material Preparation method Detection method Working potential Limit of detection Linear range Interferences Real sample Ref.
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