Accepted Manuscript

Accepted Manuscript Nanomaterial-based electrochemical sensors for the detection of neurochemicals in biological matrices Abdelmonaim Azzouz, K.Yugender Goud, Nadeem Raza, Evaristo Ballesteros, SungEun Lee, Jongki Hong, Akash Deep, Ki-Hyun Kim PII:

S0165-9936(18)30279-6

DOI:

10.1016/j.trac.2018.08.002

Reference:

TRAC 15212

To appear in:

Trends in Analytical Chemistry

Received Date: 8 June 2018 Revised Date:

6 August 2018

Accepted Date: 8 August 2018

Please cite this article as: A. Azzouz, K.Y. Goud, N. Raza, E. Ballesteros, S.-E. Lee, J. Hong, A. Deep, K.-H. Kim, Nanomaterial-based electrochemical sensors for the detection of neurochemicals in biological matrices, Trends in Analytical Chemistry (2018), doi: https://doi.org/10.1016/j.trac.2018.08.002. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT 1 2 3

Nanomaterial-based electrochemical sensors for the detection of neurochemicals

4

in biological matrices

6 7

RI PT

5

Abdelmonaim Azzouz1, K Yugender Goud2, Nadeem Raza3, Evaristo Ballesteros1, Sung-Eun Lee5, 7 2* Jongki Hong6, Akash Deep *, Ki-Hyun Kim

8 1

Department of Physical and Analytical Chemistry, E.P.S. of Linares, University of Jaén, E-23700

SC

9 10

Linares, Jaén, Spain

11

2

12

Seoul, 04763, Korea

13

3

Govt. Emerson College affiliated with Bahauddin Zakariya University Multan, Pakistan

14

4

School of Applied Biosciences, Kyungpook National University, Daegu 41566, Korea

15

5

College of Pharmacy, Kyung Hee University, 26 Kyungheedae-ro, Seoul, 02447, Korea

16

7

Nanoscience and Nanotechnology Lab, Central Scientific Instruments Organisation (CSIR-CSIO),

17

Sector 30 C, Chandigarh 160030, India

M AN U

TE D

EP

19

AC C

18

Department of Civil and Environmental Engineering, Hanyang University, 222 Wangsimni-Ro,

1

ACCEPTED MANUSCRIPT 20

Abstract Neurochemicals such as dopamine, glutamate, GABA, adenosine, and serotonin are efficient

22

indicators for quantifying the dynamics of many brain disorders. Both in vivo and in vitro detection

23

strategies for those neurochemicals are important in treating various human diseases. Along with

24

common, conventional tools (e.g., microelectrodes, biosensors, spectrophotometry, Fourier

25

transform infrared, Raman, chromatography, fluorescence, flow injection, and capillary

26

electrophoresis), electrochemical sensors based on nanomaterials (NMs; e.g., graphene, carbon

27

nanotubes, molecular imprinted polymers, metal organic frameworks, and metallic nanoparticles)

28

have emerged as potent tools for the quantitation of neurochemicals due to their robust designs,

29

selectivity, sensitivity, precision, and accuracy. The performance of the latter varies widely because

30

of differences in their sensing efficiencies. This review provides a brief introduction to those

31

electrochemical sensors with a detailed overview of the latest trends, limitations of NM-based

32

sensing techniques, and the potential for their future expansion for various neurochemicals.

SC

M AN U

TE D

33

RI PT

21

Keywords: Nanomaterials; Neurochemicals; Electrochemical sensors; Dopamine; Molecularly

35

imprinted polymers; Metal organic frameworks

36

Corresponding author: [email protected]; [email protected]

38

AC C

37

EP

34

2

ACCEPTED MANUSCRIPT

Contents

40

1. Introduction

41

2. Neurochemicals

42

3. Electrochemical sensors based on nanomaterials 3.1. Graphene and graphene oxide

44

3.2. Carbon nanotubes

45

3.3. Metal organic frameworks

46

3.4. Molecularly imprinted polymers

47

3.5. Other materials (Metallic nanoparticles)

M AN U

43

SC

RI PT

39

48

4. Performance comparison between different sensing methods

49

5. Conclusion and outlook

TE D EP

51

References

AC C

50

3


53

1. Introduction It is well established that disorders of the central nervous system (CNS) (e.g., depression,

54 schizophrenia, Alzheimer’s disease, Parkinson’s disease, and certain types of cancer) account for a

RI PT

55 significant percentage of global healthcare costs, about 800 billion Euros [1]. In other words, such 56 disorders not only affect the overall health of society, but also consume many economic resources 57 [1]. CNS disorders are characterized by neuropathological function changes and progressive decline 58 in cognitive capacities as a result of volume loss and neurochemical alterations [2]. It has been

SC

59 reported that imbalances in neurochemicals (NCs) such as hypoxanthine, xanthine, serotonin (5-HT),

M AN U

60 uric acid (UA), dopamine (DA), ascorbic acid (AA), norepinephrine (NE), epinephrine (EP), 61 acetylcholine, and gamma-amino butyric acid (GABA) can influence or propagate several CNS 62 disorders [3-5]. The physiological levels of some NCs in biological fluids vary significantly with the 63 progression of neuronal diseases due to the changing activity and concentrations of metabolic 64 enzymes [6]. Therefore, the identification of NCs and their biomarkers in biological fluids is

TE D

65 important for the diagnosis, treatment, and prognosis of neurological disorders. NC profiling from 66 biological samples is challenging because of the very different polarities of NCs, their low

EP

67 physiological levels, and high matrix interference [6]. To meet current healthcare needs, therefore, 68 the development of rapid, highly sensitive and accurate, and low-cost detection methods for NCs is

70

AC C

69 highly desired.

Several reports have been published about the use of traditional analytical techniques (such as

71 chromatography, colorimetry, and spectroscopy) along with portable sensors (electrochemical, 72 optical, etc.) for the analysis of NCs. The sensors have many benefits over the conventional 73 analytical tools in terms of cost, sensitivity, rapidity, and convenience of operation. In particular, 74 electrochemical sensors based on nanomaterials (NMs) can further benefit by enhancing the 75 selectivity for NCs [8]. Many studies have been carried out to develop electrochemical sensors that 4

ACCEPTED MANUSCRIPT 76 use diverse NMs for the accurate analysis of NCs. The most important systems in this context are 77 based on NMs such as graphene, carbon nanotubes (CNTs), metal organic frameworks (MOFs), and 78 molecular imprinted polymers (MIPs).

Graphene-based nanostructures, including graphene oxides and doped graphene (oxides), have

RI PT

79

80 been widely used as platforms for sensors that display high sensitivity, selectivity, and stability [7]. 81 For example, Raji et al. used a nano-composite of graphene and a conducting polymer to modify a 82 screen-printed carbon electrode for concurrent assessment of DA and 5-hydroxytryptamine in human

SC

83 blood and urine samples [8]. Likewise, Song et al. used a sensor based on carbon-encapsulated

M AN U

84 hollow magnetite (Fe3O4) nanoparticles and graphene oxide (GO) nanosheets to assess UA and DA 85 in rat brain tissue, whole blood, and urine samples [9]. A molybdenum (Mo)-doped reduced graphene 86 oxide (RGO)/polyimide composite was used to analyze DA in human serum and injection samples 87 [10]. CNT-based electrochemical sensors could display a low limit of detection (LOD) in 88 combination with fast response though the signal enhancement provided by their desirable electrode

TE D

89 properties of rapid response, high surface area, and low overvoltage [11]. CNTs also offer high 90 thermal conductivity, good mechanical strength, and chemical stability, which are appealing

EP

91 properties for electrochemical sensing applications. Sun et al. used a NiO/CNT/poly(3,492 ethylenedioxythiophene) composite with a coaxial tubular nanostructure to detect 5-HT and DA

AC C

93 tryptophan (Try) in human serum [11]. Tiwari et al. used CNTs for the electrochemical determination 94 of several biomolecules (glucose, H2O2, UA, DA, DNA, RNA, and proteins, including enzymes) 95 [12]. Tan et al. used hybrid films of multiwall carbon nanotubes (MWCNTs) and boron-doped 96 ultrananocrystalline diamond to fabricate a microsensor for DA in the presence of some commonly 97 associated interfering species [13].

98

MIPs have also attracted much attention as electrochemical sensors for clinical applications such

99 as the determination of multianalyte neurotransmitters, DA, NE, and EP [14,15] in serum and brain 5

ACCEPTED MANUSCRIPT 100 tissue. Pacheco et al. used a MIP electrochemical sensor to analyze a breast-cancer biomarker (cancer 101 antigen A 15-3) [16]. Magnetic MIPs have also been coupled with electrochemical sensors to 102 determine the NCs in diverse media samples [17].

As a moderately new class of advanced porous materials, MOFs might also be useful in the

RI PT

103

104 construction of electrochemical sensors. For example, an electrochemical sensor was developed 105 based on the electro-catalytic oxidation of L-cysteine (L-cys) [18]. Similarly, a porphyrinic 106 MOF/macroporous carbon-composite was used for the real-time assessment of UA, hypoxanthine

SC

107 (HX), and xanthine (XA) [19]. The DA content in human urine and DA hydrochloride injection

M AN U

108 samples was analyzed using an Fe-MIL-88 metal-organic frameworks–hydrogenperoxide– 109 ophenylenediamine (Fe-MIL-88–H2O2-OPD) system. [20]. 110

Other nanoparticles have also been used as electrochemical sensors. For example, a glassy carbon

111 electrochemical sensor modified with gold nanoparticles (AuNPs) was used to detect DA in human

TE D

112 serum [21]. Likewise, ZnO nanotubes were used for the electrochemical detection of DA in human 113 urine samples [22]. TiO2 nanotube photonic crystals were used as a photoelectrochemical sensing 114 platform for the sensitive and selective detection of DA released from mouse brains [23]. Li et al.

117

AC C

116 sensing of DA [15].

EP

115 developed an imprinted silica matrix-poly(aniline boronic acid) hybrid for the electrochemical

As shown by those examples, the application of NMs as electrochemical sensors has garnered the

118 attention of many research groups. Researchers have reviewed the applications of such sensors to 119 different analytes. For example, Li et al. reported the mechanisms, characteristics, and performance 120 of some pure metals (Au, Cu, Ni, Pd, and Pt), metal oxides (CuOx, ZnO, NiO, TiO2, and Co3O4), and 121 carbon (nanotubes and graphene) NMs for enzymatic/non-enzymatic glucose and H2O2 122 electrochemical applications [24]. Kempahanumakkagari et al. reviewed the classification, 123 preparation, and applications of MOF-based electrochemical and biological sensors for the 6

ACCEPTED MANUSCRIPT 2+

2+

124 quantitation of various environmentally and biochemically important analytes, such as Pb , Mn , 125 BrO3, NO2, phenol isomers (catechol (CT), resorcinol, and hydroquinone (HQ)), glucose, reduced 126 glutathione (GSH), L-cys, and H2O2 [25].

Other researchers have reviewed the fundamentals of electron transfer in carbon NMs and the

RI PT

127

128 synthesis and application of various 2D graphene-based electrochemical sensors for H2O2 [26]. In 129 particular, they summarized the available information about various graphene-based nanoplatforms 130 that work efficiently as an immobilization matrix to support heme protein loading. Those systems can

SC

131 be useful electrochemical biosensors for the enzymatic detection of H2O2. Yang et al. also discussed

M AN U

132 issues with the practical implementation of those sensors [26]. Additionally, the use of graphene133 based electrocatalysts (metal-free, noble-metals, and non-noble metals) for the development of non134 enzymatic H2O2 electrochemical sensors has been discussed in detail [27]. Furthermore, Rivas et al. 135 discussed the (bio) recognition element, preparation of the (bio) recognition layer, the strategy for 136 transducing the (bio) affinity event, and the analytical performance of biosensors for the

TE D

137 quantification of different biomarkers [28]. Recent progress in NM-based electrochemical (bio) 138 sensors was described in another review that focused on the in vitro detection of reactive oxygen

EP

139 species and glucose levels [29]. That review also discussed the exploration of lightweight 140 (micro/nanoscale) and flexible electrodes for the realization of miniaturized sensors.

In this review, we describe advances in the growth of NM-based electrochemical sensor and

AC C

141

142 biosensor systems for the detection of biologically/biomedically important analytes that are 143 commonly present in clinical, pharmaceutical, biomedical, and biological fluids [30]. We focus 144 mainly on the growth of NM-based electrochemical sensors for the neurotransmitters and NCs 145 present in biological fluids (e.g., DA, AA, and 5-HT; H2O2; biomarkers; DNA), highlighting the 146 latest developments in electrochemical sensors based on NMs such as CNTs, graphene, GO, MOFs, 147 MIPs, metals, and metal oxides. We also provide the latest information on enzyme-based electrodes, 7

ACCEPTED MANUSCRIPT 148 which have proved useful for the detection of non-electroactive species such as proteins, alcohols, 149 and glucose. Finally, we analyze the future directions in this field, identifying the research gaps. Our 150 results will help researchers determine how advanced NMs could be used in the fabrication of highly 151 efficient electrochemical sensor and biosensor platforms for the sensitive detection of CNS diseases,

RI PT

152 which will expedite the application of appropriate medical therapies. Due to their intriguing features, 153 MOF- and MIP-based electrochemical sensors currently have the interest of several research groups.

SC

154

155 2. Neurochemicals

NCs are chemical substances secreted or produced in different parts of the body. They play vital

M AN U

156

157 roles, such as activating behavioral patterns and tendencies in specific regions of the brain [31]. NCs 158 regulate emotions and thoughts, promote the growth and repair of the nervous system (NS), and 159 transmit signals. It is well established that the proper working of NCs in the body is greatly affected

TE D

160 by their regulated levels in the bloodstream and elsewhere. Their levels are controlled by feedback 161 mechanisms, and an inability to produce or absorb NCs in the proper amounts can result in issues 162 ranging from psychosis to Alzheimer’s disease. The proper functions of NCs are generally related to

EP

163 their chemical structure, levels in the bloodstream, and the presence or absence of drugs that can alter

165

AC C

164 their chemical effectiveness [30].

NCs can be classified in several ways. For example, on the basis of chemical composition, NCs

166 can be classified as small molecules (DA, 5-HT, and GABA), neuropeptides (insulin, oxytocin, and 167 vasopressin), or gasotransmitters (carbon monoxide and nitric oxide). NCs can also be grouped as 168 neurotransmitters, neuromodulators, and neurohormones [32]. However, on the basis of function, 169 NCs are categorized as inhibitory (glycine, DA, and 5-HT), excitatory (glutamate, nitric oxide, and 170 aspartate), or both. Collectively, all these different types of NCs constitute complicated interactive

8

ACCEPTED MANUSCRIPT 171 networks that govern and regulate neuron activities such as learning, memory, reward, cognition, 172 emotion, addiction, and stress response. A list of NCs and their physiochemical characteristics is 173 given in Table 1.

Neurotransmitters (NTs), one major class of NCs, cross the synapses between neurons to transmit

RI PT

174

175 signals. They are packed in intracellular vesicles and excreted from synapses through exocytosis 176 upon chemical or electrical stimulation [32]. Excreted NTs respond to specific receptors and trigger 177 chemical cascades in target cells. Given the complexities of NCs and to maintain the conciseness of

Glutamate is one of the most abundant NTs in the human body and is involved in learning and

M AN U

179

SC

178 this article, we describe only a few NCs below.

180 memory. It is the major excitatory NT in the CNS and is an agonist at both ionotropic and 181 metabotropic glutamate receptors. Excessive levels can poison nerve cells and result in mental 182 retardation, stroke, seizures, and Lou Gehrig’s disease [33]. DA is found in both the CNS and the

TE D

183 peripheral NS [34]. It is a small-molecule NT in the class of biogenic amines and governs several 184 brain-related functions, including memory, voluntary motor control, and motivation. DA is also an 185 important factor in the brain's reward system, influencing pleasurable sensations via stimulation by

EP

186 food, sex, and other sources of enjoyment. Insufficient DA level is implicated in Parkinson's disease, 187 schizophrenia, deficits in the sense of smell, prolactin secretion, emesis, attention-deficit

AC C

188 hyperactivity disorder, motor control problems (e.g., tremor and slowed movements), and drug 189 dependence [1]. In the peripheral regions, DA governs diverse body activities such as pyloric 190 sphincter tone and gastric motility, light–dark adaptation in the retina, and autonomic/cardiac 191 function [34].

192

Serotonin is a monoamine NT that manages the digestive system and an organism's perception of

193 resources such as food. It also plays a significant role in mental processes, social power, dominance,

9

ACCEPTED MANUSCRIPT 194 submission, depression, mania, mood, and cognition, and it is implicated in many psychiatric 195 disorders [35].

196

3. Electrochemical sensors based on nanomaterials

RI PT

197

Electrochemical sensors have been extensively employed for the detection purposes in diverse

199

fields of life (e.g., environmental, food, pesticides, and pharmaceutical/clinical applications) [36-

200

38]. In such applications, electrochemical sensors are deployed to transform electrochemical

201

information into useful signals. A typical working electrochemical sensor consists of two main

202

parts: (1) chemical recognition system and (2) physicochemical transducer (which converts

203

chemical responses into a signals that could be detected easily by modern electrical instruments)

204

[39,40].

M AN U

SC

198

In recent years, important studies have considered NM-based electrochemical sensors with

206

significant applications for NC sensing. Based on their superior sensing performance compared

207

with other analytical techniques, electrochemical sensors based on diverse materials (e.g., MOFs,

208

graphene, CNTs, MIPs, metals, and metal oxides) are currently in wide use for proteins, antibiotics,

209

pesticides, NCs, hormones, etc. In this section, we summarize recent advances in MOF-, graphene-,

210

CNT-, MIP-, metal-, and metal oxide–based electrochemical sensors for NCs.

211

212 3.1.

AC C

EP

TE D

205

Graphene and graphene oxide

213

Graphene is an emerging carbon NM that has attracted significant attention from scientists and

214

technologists during the past decade. Graphene has many fascinating physical and electrochemical

215

characteristics and has been broadly used as an electrode in highly efficient electrochemical sensors. 10

ACCEPTED MANUSCRIPT Graphene exhibits some remarkable properties, such as high conductivity, mechanical strength, high

217

surface area, and a catalytic nature. Moreover, graphene shows minimal charge-transfer resistance

218

and enhanced electrochemical activity due to its large potential window for fast electron transfer

219

rates. Recent developments in graphene-based electrochemical sensors for neurotransmitters are

220

summarized in Table 2. GO and RGO, alone and as part of metal/metal oxide nanoparticle

221

nanocomposites, are good transducer platforms for electrochemical sensing.

RI PT

216

A glassy carbon electrode (GCE) altered electrochemically with (partial) RGO has been constructed

223

for standalone and simultaneous voltammetric determination of AA, DA, and UA [41]. The

224

researchers prepared the GO by modifying Hummer's method and used an ultrasonication process for

225

its subsequent exfoliation. Next, they used potentiodynamic cycling to control the partial

226

electrochemical reduction into RGO. The resulting material was then cast on the exterior of the GCE.

227

The resulting electrochemical sensor offered a broad range of linearity against AA, DA, and UA in

228

concentration ranges of 4×10-5 to 1×10-3 M (LOD = 4.2×10-6 M), 1×10-7 to 1×10-4 M (LOD = 8×10-9

229

M), and 8×10-7 to 8×10-4 M (LOD = 6×10-7 M), respectively.

TE D

M AN U

SC

222

A highly sensitive electrochemical sensor for DA was made by exploiting a GCE interface

231

containing ionic-liquid-functionalized GO-supported gold nanoparticles (GO-IL-AuNPs) [42] (Fig

232

1). Using differential pulse voltammetry as the transduction method allowed the detection of ultra-

233

trace concentrations of DA within a linear range of 7 nM to 5 mM (LOD = 2.3 nM). That sensor also

234

provided accurate quantification of DA in real samples. Incorporating noble metal NMs into

235

graphene nanosheets could improve the electronic, chemical, and electrochemical properties of a

236

transducer system. Li et al. reported an electrochemical voltammetric sensor for the detection of DA

237

utilizing composites of palladium@gold nanoalloys and nitrogen and a sulfur-functionalized multiple

238

graphene aerogel (Pd@Au/N, S-MGA) [43]. The unique structure of the GCE-Pd@Au/N,S-MGA

239

electrode interface achieved ultra-high electron conductivity, good electrocatalytic activity, and

AC C

EP

230

11


structural stability. Differential pulse voltammetry–based analysis exhibited good linearity for the

241

electrochemical signal of the analyte (DA) in the range of 1.0×10-9 M to 4.0×10-5 M (LOD = 3.6 ×

242

10-10 M). An electrochemical amperometric sensor was prepared by modifying a GCE with various graphene-

244

based NMs and deployed to detect 5-HT [44]. The researchers synthesized three types of RGO in the

245

presence of different reducing species (hydrazine, hydrazine-ammonia solution, and hydroxyl amine-

246

ammonia solution). Quantitative detection of 5-HT was carried out in the concentration range of 1–36

247

µM; a good LOD (3.2×10-8 M) was observed with the RGO made using the hydrazine-ammonia

248

solution. Conducting polymer-based NM transducer systems have demonstrated prompt and precise

249

detection of various targets because of their structural homogeneity, availability of active site,

250

environmental stability, and tendency for strong interactions with the electrode surface. Thus, these

251

systems often deliver high selectivity and sensitivity. A hybrid nanocomposite of poly(3, 4-

252

ethylenedioxythiophene) (PEDOT), RGO, and silver nanoparticles was used to modify a GCE into a

253

new transducer platform (PEDOTNTs/RGO/AgNP/GCE) for the detection of 5-HT [45]. Its

254

performance was studied using cyclic voltammetry (CV), differential pulse voltammetry (DPV), and

255

chrono-amperometry (CA). In particular, the DPV analysis found that the sensor had a low detection

256

limit (0.1 nM) and a wide linear range of analysis (1 nM to 0.5 mM).

257

258 3.2.

AC C

EP

TE D

M AN U

SC

RI PT

243

Carbon nanotubes

259

Electrochemical sensing platforms have widely exploited CNTs as an efficient electrode material.

260

Due to their excellent electron transfer ability, large surface area, and favorable structural,

261

mechanical, and electronic properties, CNTs provide strong electro-catalytic activity and high

262

sensitivity. CNTs also provide excellent immobilization of biorecognition elements such as 12

ACCEPTED MANUSCRIPT antibodies, aptamers, enzymes, and imprinted polymers. Single-walled CNTs (SWCNTs), multi-

264

walled CNTs (MWCNTs), and their hybrid nanocomposites with metallic species are all good

265

transducers in electrochemical sensing platforms. Newly developed CNT-based electrochemical

266

sensors for NCs are described in Table 2.

RI PT

263

An electrochemical voltammetric sensor was fabricated using a GCE altered with a nanocomposite

268

of gold nanorods (GNRs) and MWCNTs (GNR/CNT/GCE) for the specific detection of DA [46].

269

Electrostatic interactions between the GNRs (+ charge) and the CNTs (- charge) stabilized the

270

electrode material. In the DPV results, the electrode sensitively quantified DA, even in the presence

271

of AA, with an LOD of 0.8 nM.

M AN U

SC

267

A carbon paste–based electrode was modified with MWCNT/poly(glycine) using DPV as the

273

transduction method and tested for its detection of DA [47]. It successfully detected DA in a linear

274

dynamic range of 5.0×10−7 M to 4.0×10−5 M, with a good LOD of 1.2×10−8 M. Its practicality was

275

confirmed by demonstrating the analysis of DA in samples of human blood serum and a

276

hydrochloride injection.

TE D

272

A composite was prepared by decorating magnetic metal nanoparticles with MWCNTs (NiFe2O4-

278

MWCNT), and it was then cast on a GCE to prepare a sensor (NiFe2O4-MWCNT-GCE) for DA [48].

279

The resulting electrode catalyzed the oxidation of DA through synergic effects. In DPV

280

measurements, the oxidation peak current exhibited a linear increase as the DA amount increased

281

through two distinct concentration ranges, 0.05–6.0 and 6.0–100 µmol L−1. The LOD for the method

282

was 0.02 µmol L−1.

AC C

EP

277

283

A nano-bio-composite-based electrochemical sensor (MWCNT-Chit composite modified GCE)

284

has been developed for the accurate quantification of 5-HT in the presence of DA and AA [49] (Fig

13


2). The DPV technique attained a linear calibration plot (5×10-8 – 1.6×10-5 M) with a low LOD of

286

5×10-8 M for 5-HT. Another sensor used an electrodeposited composite of colloidal AgNOs, MWCNTs, and

288

polypyrrole (PPy) on a platinum (Pt) electrode surface for the detection of 5-HT [50], with DPV as

289

the transduction method. Under optimized conditions, the Pt/MWCNT/PPy/AgNP electrode for 5-HT

290

showed an LOD of 0.15 µmol L−1.

RI PT

287

The electrochemical detection of 5-HT was carried out using MWCNT-doped nickel, zinc, and

292

iron-oxide nanoparticles (NPs) on a GCE [51]. CV and square wave voltammetry (SWV) were used

293

as the transduction methods. 5-HT detection was achieved in the concentration range of 5.98×10−3

294

µM to 62.8 µM, with corresponding detection limits of 129, 118, and 166 nM using the

295

GCE/MWCNT-ZnO, GCE/MWCNT-NiO, and GCE/MWCNT-Fe3O4 sensors, respectively.

M AN U

SC

291

296

298

Metal-organic frameworks

TE D

297 3.3.

MOFs are highly investigated porous coordination polymers that have received significant

EP

299 consideration in the development of electrochemical sensors because of their unique characteristics, 300 such as a large surface area with ultrahigh and tunable porosity, high thermal and chemical stabilities,

AC C

301 and excellent catalytic properties [119]. Those characteristics of MOFs have primarily been exploited 302 in bioimaging and sensing, catalysis, molecular filtration, and gas storage. Post-synthetic chemical 303 alterations of MOFs produce other characteristic features that make it possible to fabricate a new 304 generation of electrochemical/optical sensors. MOFs show better biocompatibility than inorganic 305 NMs (e.g., graphene). Therefore, they are potentially better candidates for both in vivo and in vitro 306 analyses of biological analytes. In fact, for special applications, MOFs can even be assembled with 307 biocompatible building blocks [120]. A huge mass of literature demonstrates the great interest within 14

ACCEPTED MANUSCRIPT 308 the research community for the exploration of MOFs for both luminescent and electrochemical 309 sensors. In one of the very first investigations [121], used MOFs to prepare an impedance signal310 based sensor for small molecules. Later, Mao et al. used MOFs to design an integrated

312

RI PT

311 dehydrogenase-based electrochemical biosensor for the in vivo measurement of NCs [122].

Many MOF-based electrochemical sensors have been developed for the detection of NCs in

313 recent years (Table 3). Zheng et al. synthesized graphene-zeolitic imidazolate frameworks (G-ZIF-8) 314 by soaking 3D graphene templates in a methanolic solution of Zn2+ ions. Subsequently, they

SC

315 introduced those metal ion-containing templates to a solution of 2-methylimidazole and used

M AN U

316 solvothermal-assisted molecular diffusion to enhance the growth of the ZIF-8 crystals over the 3D 317 graphene sheets (G-ZIF8) [123]. A modified electrode (G-ZIF8/GCE) was then fabricated by 318 introducing a few milliliters of the G-ZIF-8 suspension onto a GCE. The electrode showed good 319 electro-analytical performance for DA, with a linear concentration range from 3.0 µM to 1000 µM 320 and detection sensitivity and an LOD of 0.34 µA/mmol/L and 1.0 µM, respectively. They also tested

TE D

321 the electrode for interference, stability, and reproducibility and found that it could detect DA in cow 322 serum samples with recoveries from 96.8 % to 100.7 % [123]. Zhao et al. developed a sensor based

EP

323 on the turn-on fluorescence of an Fe-MIL-88–H2O2-OPD system to analyze the DA in a 324 hydrochloride injection and human urine [20]. The linear range of detection was 0.050 to 30 µM,

326

AC C

325 with an LOD of 0.046 µM.

RGO was used as a template for the synthesis of a hybrid nanocomposite of RGO/ZIF-8 during

327 the in situ growth of ZIF-8 (Fig. 3A) [124]. The characterization of ZIF-8, GO, RGO, and RGO/ZIF328 8 were carried out by SEM and XRD (Fig. 3B and 3C). The electrocatalytic activity of the above 329 nanocomposite electrode toward DA was investigated using CV and DPV. The RGO/ZIF-8 sensor 330 exhibited high sensitivity, which was attributed to the synergistic effect of the high electrical 331 conductivity of RGO in combination with the porosity of the ZIF-8. At optimized experimental 15

ACCEPTED MANUSCRIPT 332 parameters, the linear range of the deployed sensor to DA was from 0.1 to 100 µM with an LOD of 333 0.03 µM (Fig. 3D) [124].

334

Yin et al. reported the formation of a porphyrinic (Zr-Pro) MOF-based composite using a

RI PT

335 simple one-step solvothermal method that grew Zr-PorMOF on macroporous carbon (MPC) [19]. 336 Thereafter, they dispersed 3 mg of each of three materials, Zr-PorMOF, MPC, and Zr337 PorMOF/MPC-x, in 1 mL of Nafion (0.1 wt %) and sonicated the mixtures for 30 min before drop338 casting 5 mL of each solution onto the surface of a GCE and allowing the modified electrode to dry

SC

339 in air. The DPV results showed high current and sensitivity, so they tested the electrocatalytic activity

M AN U

340 of the tZr-PorMOF/MPC composites for UA, XA, and HX oxidation. They found that the Zr341 PorMOF/MPC composites reduced H2O2 better than Zr-PorMOF. They attributed that behavior to 342 synergic interactions between the Zr-PorMOF and MPC. That non-enzymatic sensor showed wide 343 linear ranges of detection, 5–160 µM, 5–200 µM, and 5–220 µM for UA, XA, and HX, respectively, 344 and had other useful features, such as a low over-potential (– 0.2 V), rapid response ( ≤ 1 s), and low

346

TE D

345 LODs (0.49 µM for all analytes) [19].

A GCE electrode was modified with Nafion/C/Al-MIL-53-(OH)2 for the detection of DA [125].

EP

347 C/Al-MIL-53-(OH)2 was suspended in N,N-dimethyl formamide and agitated for 60 min. The 348 dispersion was then used to modify a bare GCE. As the solvent evaporated, the electrode was coated

AC C

349 again by introducing a 5 mL Nafion solution (0.5%). After drying, the resulting Nafion/C/MIL-53350 (OH)2/GCE electrode was used as an electrocatalyst for DA oxidation in serum and urine samples 351 [125]. It demonstrated a remarkable voltammetric response toward DA due to the combined effects 352 of the different materials: the large surface area of the Al-MIL-53-(OH)2, high conductivity of the 353 carbon, and formation of a sensor film through the addition of Nafion. The response peak currents 354 exhibited good linearity with analyte concentrations from 0.03 to 10 µM. The LOD for DA was 8.0 355 nM [125]. ZIF-8 nanocrystals (mean diameter of 260 nm and Brunauer-Emmett-Teller surface area 16


−1

356 of 1495 m g ) was also synthesized using an ultrasonic-assisted solvothermal method [126]. They 357 then used those crystals to modify GCE electrodes whose electrocatalytic properties they explored for 358 the CV, DPV, and amperometric detection of DA. The sensor offered detection within linear ranges

360

RI PT

359 of 0.05–0.5 µM and 1.0–20.0µM, with a low LOD of 0.195 µM [126].

An “on-off” electrochemiluminescence (ECL) sensor was proposed for the quantification of DA

361 by adopting the dual molecular recognition strategy [127]. Their method involved the quenching 362 effect of Fe-MIL-88 in the presence of a 3,4,9,10-perylenetetracar-boxylic acid (PTCA)-H2O2

SC

363 system. The LOD of the system was 2.9×10−7 µM. The PTCA-H2O2 system was suggested as a new

M AN U

364 ECL platform, particularly for the realization of enzyme-based ECL sensors [127]. Another group of 365 researchers developed a sensor using a relatively water-resistant MOF {[Cd(µ3-abtz)·2I]}n (Abtz– 366 CdI2–MOF, abtz = 1-(4-aminobenzyl)-1,2,4-triazole) that they synthesized using solvothermal 367 techniques [128]. The proposed system served as an “off–on” fluorescent switch to allow label-free 368 detection of DA and did not require any specific functionalization or modifications. The relative

TE D

369 intensity of the fluorescence restored was reflected by the analyte concentration in a wide linear 370 range (0.25–50 µM) with a low LOD (0.057 µM). Importantly, many potential interfering substances

372

EP

371 (e.g., glucides, AA and UA, amino acids, metal ions) did not affect the results [128].

A sensor was prepared with CNTs implanted with manganese-based MOFs and used to detect AA,

AC C

373 DA, and UA in body fluids [129]. The addition of MWCNTs initiated the exfoliation of bulky Mn374 BDC into thin layers. The sensor had linear detection ranges of 0.1–1150, 0.01–500, and 0.02–1100 375 µM for AA, DA, and UA, respectively. Low LOD values were also achieved: 0.01, 0.002, and 0.005 376 µM for AA, DA, and UA, respectively [129].

377

A MIL-101 carbon paste electrode (CPE) was reported for sensing DA and UA based on

378 electrocatalytic oxidation [130]. The sensor material was fabricated by mixing paraffin and graphite 379 powder with MIL-101. The resulting paste was tightly packed into the hole of an electrode body, 17

ACCEPTED MANUSCRIPT 380 with a copper rod used as the inner electrical contact. The sensor features were characterized by 381 electrochemical impedance spectroscopy and CV. The linear range for the detection of DA and UA 382 was 5–250 µM and 30–200 µM, respectively [130].

Similarly, Zhang et al. prepared a sensor with a nanohybrid material of UiO-66-NO2@XC-72

RI PT

383

384 and used it to simultaneously detect AA, DA and UA in urine and hydrochloride injection solution 385 samples [131]. They synthesized the UiO-66-NO2 using a hydrothermal method and then mixed it 386 with XC-72 carbon. The resulting sensor electrode (UiO-66-NO2@XC-72/GCE) offered excellent

SC

387 performance in various terms. For example, the estimated peak currents of the composite electrodes

M AN U

388 were 4.2, 7, and 1.6 times higher than the bare electrode, the XC-72, and the MOF-modified GCE, 389 respectively, and peak separation of the composite electrodes was also higher that than of the XC390 72/GCE, the bare GCE, and UIO-66-NO2/GCE. When they used the sensor to detect DA in a 391 hydrochloride injection solution and UA in urine samples, they recovered 101.3% and 100.7%, 392 respectively. The LODs for AA, DA, and UA were 0.12, 0.005, and 0.03 µM, respectively, with

394

TE D

393 linear ranges of 0.2–3.5 µM, 0.03–2 µM, and 0.75–22 µM [131].

A composite of vanadium-substituted phosphomolybdate and MIL-101 (PMo10V2@MIL-101 (Cr))

EP

395 was used for the electro-catalytic oxidation of AA and DA [132]. The researchers prepared the 396 composite by encapsulating the tetrabutylammonium salt of [PMo10V2]5-(PMo10V2) into the porous

AC C

397 MOF MIL-101(Cr) and then using it to modify pyrolytic graphite electrodes. They used a CV-based 398 analysis of AA and DA and found respective linear ranges of 0–0.09 µM and 0–0.03 µM [132]. 399 Despite several benefits associated with MOF‐based electrochemical sensors, they have certain 400 limitations in terms of (1) conductivity of MOFs and the design of redox‐active MOFs as most MOF 401 materials are insulators or semiconductors, (2) poor binding of targets to MOF sensing surfaces due 402 to lack of proper functionalities, (3) deficiencies in target selectivity, and (4) long response time due 403 to their unsuitable dimensions for rapid analyte uptake and equilibration. 18


405 3.4.

Molecularly imprinted polymers MIPs are now considered a pivotal tool in several fields such as medical diagnosis, biological

407

analysis, food safety evaluation, and environmental monitoring. Due to their capacity for highly

408

specific recognition for target biomolecules, MIP-based electrochemical sensors have been used

409

extensively in electrochemical sensing applications in recent years and exhibit some important

410

superiorities over other analytical techniques, such as high selectivity and sensitivity,

411

chemical/mechanical stability, reusability, low LODs, facile preparation, and low cost [139].

412

Generally, MIPs are obtained by bulk (3D) polymerization, a process in which functional

413

monomers (organic or inorganic materials) are polymerized around a target template in the presence

414

of cross-linking agents. The template molecule is extracted after polymerization, and a polymer

415

matrix with distinctive features (such as sites complementary to the imprinted molecule in

416

functionality, shape, and size) is separated. MIPs show specific affinity toward the template

417

molecule [16]. Various electrosynthesized MIPs have been developed on different electrode

418

surfaces, e.g., poly(pyrrole)(Ppy), Ppy–phenyl boronic acid, poly bis(2,2-bithienyl) methane

419

derivatives, and poly(o-aminophenol). These electrochemical sensors have been used for the

420

selective detection of NCs in the presence of structural analogs and other interfering species [4].

AC C

EP

TE D

M AN U

SC

RI PT

406

421

In recent years, many studies have reported MIP-based electrochemical sensors for NC detection

422

(Table 3). Li et al. used a modified MIP (nicotinamide)/CuO NP electrode to sense DA in serum.

423

They used nicotinamide as the monomer to grow MIPs on the surface of a CuO NP-coated GCE

424

[140]. Their MIP sensor could assay DA in the 0.02–25 µM range, with a low LOD of 0.008 µM.

425

They used the system to analyze spiked samples and achieved recoveries from 96.9% to 105.9%

426

[135]. An MIP-based electrochemical sensor was prepared for DA detection using pyrrole

427

phenylboronic acid (Py-PBA) as the functional monomer [141]. Using DA as the template, Py-PBA 19

ACCEPTED MANUSCRIPT was electro-polymerized as an MIP on a GCE. Thus, the prepared poly(Py-PBA)/GCE sensing

429

system could recognize DA even in the presence of its analogs and other monosaccharides. The

430

linear range of analysis for the detection of DA was 0.05 to 10 µM, with an LOD of 0.033 µM. The

431

sensor could also analyze DA in injection samples [141].

RI PT

428

A modified GCE was developed using a molecularly imprinted silica (MIS) film prepared by the

433

electro-assisted deposition of sol-gel precursors [142]. The MIS-modified GCE had high selectivity

434

for DA assessment. Li et al. reported a sensor for EP that used 3D MIP arrays as the sensing

435

material, which they developed via electro-polymerization of pyrrole onto ZnO nanorods (ZNRs)

436

and an ITO/PET substrate in the presence of EP (as the template molecule) [15]. Based on the

437

measurement of oxidation peak current (DPV method), EP was detectable in two linear dynamic

438

ranges (1–10 µM and 10–800 µM). They used their sensor to investigate EP in epinephrine

439

hydrochloride injection samples and obtained good recoveries, from 97.1 to 102.2% [15]. In another

440

investigation, the same research group reported an imprinted silica matrix-poly(aniline boronic

441

acid)–based hybrid sensor to detect DA [143]. The imprinted hybrid sensor showed a quick

442

response (within 5 min) to DA in a concentration range of 0.05 to 500 µM, with an LOD of 0.018

443

µM. The mean recoveries in that study were 98–106 % [143].

EP

TE D

M AN U

SC

432

A biomimetic electrochemical sensor built using polythioaniline-bridged gold NPs was reported

445

[144]. This sensor was prepared by single-step CV-assisted polymerization of thioaniline and

446

generation of AuNPs in the presence of the target molecule, DA. The researchers used CV,

447

electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), atomic force

448

microscopy, and energy dispersive X-ray spectroscopy to characterize their sensor. A DPV-based

449

analysis allowed the quantification of DA with a low LOD of 3.3x10-5 µM and a linear range of

450

detection of 0.001 to 5.0 µM [144]. Li et al. fabricated an electrode by dealloying nanoporous Au-

451

Ag alloyed microrods (NPAMR) and then using electro-polymerized poly(o-aminophenol) to create

AC C

444

20

ACCEPTED MANUSCRIPT an MIP [145]. Their MIP/NPAMR system showed a high peak current after removal of the DA

453

template. The linear range of detection was 2x10-7µM to 2x10-2 µM, with an LOD of 6.83x10-8µM.

454

They used the MIP/NPAMR sensor to detect DA in serum (rabbit) and brain tissue (rat) samples.

455

The results demonstrated excellent accuracy in detection and fairly good recovery (95% to 108%)

456

[145].

RI PT

452

A chiral electrochemical sensor was reported for sensing AA in bovine serum [146]. This sensor

458

was prepared using an electro-generated, molecularly imprinted, polymer-based ultrathin film with

459

AA as the template (Fig. 4). The researchers lauded their approach as a fast and simple protocol

460

because they did not use a carbon-dot synthesis-coating step or severe reduction conditions in the

461

polymerization cycles. The resulting sensor was highly sensitive to AA in fetal bovine serum

462

(LOD=1 µM) [146]. MIPs using PPy and o-phenylenediamine (o-PD) as functional monomers have

463

also been proposed for electrochemical sensor development. For instance, PPy-MIP and o-PD-MIP

464

were reported for the detection of multiple NCs [14]. The PPy-MIP was prepared by adding PPy

465

monomer, FeCl2, and CNTs to the template molecules (DA, NE, or EP). The o-PD-MIP was

466

prepared using electrochemical polymerization of the o-PD monomer to the template molecules

467

(DA, NE or EP). DPV-based detection of DA, NE, and EP using those MIP sensors yielded low

468

LODs (less than 13 µM). Both the DA-imprinted and EP-imprinted sensors tolerated interference

469

from closely related molecules and were therefore suggested for multi-analyte detection of multiple

470

NCs from a single sample solution [14].

AC C

EP

TE D

M AN U

SC

457

471

A sensor based on electrosynthesized 3D MIPs and polypyrrole nanowires (PPyNWs) was

472

proposed to modify a GCE for electrochemical sensing of DA in injection samples [147]. The

473

polymer-modified MIP/PPyNWs/GCE was prepared by electro-polymerization of o-PD on PPy

474

film (PPyF)/GCE in both the presence and absence of paracetamol (MIP/PPyF/GCE and non-

475

MIP/PPyF/GCE, respectively). The modified GCE had a large surface area and excellent 21

ACCEPTED MANUSCRIPT electrocatalytic activity for the oxidation of DA and offered high sensitivity. Linearity was

477

maintained in a DA range from 0.05 to 100 µM, with an LOD of 0.033 µM at a working voltage of

478

0.23 V (vs. saturated calomel electrode (SCE) under optimal conditions [147]. A ZnO nanotube

479

(ZNT)–supported MIP-array electrochemical sensor was used to detect DA in urine samples [22].

480

The ZNTs were synthesized onto a fluorine-doped tin oxide glass and used as supporting materials

481

for MIP array fabrication. When K3[Fe(CN)6] was deployed as an electron probe, the fabricated

482

electrochemical sensor exhibited dual linear dynamic ranges (0.02–5 µM and 10–800 µM) for DA,

483

with recoveries ranging from 96.0 to 106.9% [22].

SC

RI PT

476

Despite several benefits of MIPs based sensors (as discussed earlier), they also suffer from some

485

serious limitations in the analysis of NCs as described in preceding lines. It is well established that

486

MIPs are synthesized by the bulk method in a homogeneous system requiring several steps (e.g.,

487

choice of a suitable monomer and the analyte of interest to form a stable complex) which prolongs

488

the overall time of analysis [156]. Moreover, analyte-monomer interactions occurring through

489

covalent bonds allow detection of only limited analytes. Among various parameters that can

490

influence the stability of analyte–monomer complex, the selection of a suitable solvent is critical.

491

The selected solvent should not interfere in the analyte-monomer interactions. Additionally, MIPs-

492

based electrochemical sensors must have enough sensitivity towards multianalyte systems with high

493

reproducibilities.

495 3.5.

AC C

494

EP

TE D

M AN U

484

Other materials (metallic nanoparticles)

496

To date, various metallic NPs have generated tremendous research interest for their use in

497

electrochemical sensors. They show excellent conductivity, structural robustness, good mechanical

498

and electronic properties, biocompatibility, and catalytic activity [157]. Metal- and metal-oxide22

ACCEPTED MANUSCRIPT based NPs are the most popular candidates for electrochemical sensors. Examples include pure

500

metals (Au, Pd, Ni, Pt, and Cu) and metal oxides (ZnO, NiO, CuOx, TiO2, and Co3O4) [24]. For

501

sensing NCs, metal- and metal oxide NP–based electrochemical sensors have been used, as

502

summarized in Table 3. Tertiș et al [144]. prepared an electrochemical sensor based on PPy and

503

AuNPs to detect 5-HT in serum. They optimized a nanocomposite of AuNPs@PPyNPs and tested it

504

for 5-HT detection using SWV. The intensity of the peak corresponding to 5-HT oxidation showed

505

a proportional increase with increasing analyte concentration and was linear from 0.1 to 15 µM,

506

with an LOD of 0.0332 µM.

SC

RI PT

499

An electrochemical sensor of PPyNWs in combination with platinum nanoparticles (PtNPs) was

508

developed to detect DA in serum samples [158]. The template-free electro-polymerization of the

509

PPyNWs was followed by the subsequent electrodeposition of PtNPs by CV. DPV-based detection

510

of DA yielded a linear range of 1–77 µM, with a low LOD of 0.6 µM. The sensor was also used to

511

detect DA in spiked human serum samples and achieved analyte recovery of 94% [158].

TE D

M AN U

507

A recent paper reported two sensors, Au/SAM/AuNP and Au/SAM/AuNR, based on the

513

deposition of gold nanostructures over self-assembled monolayers (SAMs) [159]. The sensors were

514

prepared by first synthesizing AuNPs and gold nanorods (AuNRs) and then incorporating them into

515

a metal substrate mediated by SAMs of 4-mercaptopyridine. The CV-based electrochemical

516

response was recorded for catecholamine. The Au/SAM/AuNR displayed better activity and more

517

rapid electron shift reactions than the Au/SAM/AuNP, which in turn resulted in an increased

518

sensitivity to the oxidation rates of NA, EPI, and DA, with LODs of 6.982, 6.345, and 7.768 µM,

519

respectively. That detection method successfully tolerated the presence of AA [159].

AC C

EP

512

520

Another report used Au-ring microelectrodes (Au-RMEs) to sense DA released into samples

521

from the striatum of rats by K+. The fabrication of Au-RMEs was carried out by growing Au films

522

uniformly inside a pulled glass capillary. The sensor provided a linear range of DA analysis of 0.2– 23

ACCEPTED MANUSCRIPT 100.0 µM, with an LOD of 0.050 µM [160]. Palladium nanoparticles (PdNPs) deposited onto a

524

modified CPE and porous graphitized carbon monolith (CM) were used for the synchronized

525

assessment of AA and UA in serum samples [161]. The PdNP/CM/CPE system exhibited enhanced

526

electrochemical catalytic performance toward AA and UA compared with bare CPE, CM/CPE, and

527

PdNP/CPE. The amperometric response of the PdNP/CM/CPE yielded an LOD for AA and UA of

528

0.53 µM and 0.66 µM, respectively [161]. An electrochemical sensor of L-Cys SAMs over a

529

AuNP/MWCNT-modified GCE (L-Cys/AuNP/MWCNT/GCE) has been investigated to quantify

530

NE in human serum samples. The oxidation peak current for NE showed a linear increase within the

531

concentration range of 0.2 to 100 µM, with an LOD 0.03 µM. The sensor was also used to test NE

532

in spiked serum samples and obtained recoveries in the range of 80.7–100.2% [162].

M AN U

SC

RI PT

523

An electrochemical sensor based on NiO/CNT/PEDOT has been explored for the simultaneous

534

sensing of DA, 5-HT, and tryptophan (Trp) [11].This sensor was prepared by adding CNTs and

535

PEDOT to an aqueous solution of KCl and NiCl, followed by CV-assisted electrochemical

536

deposition of Ni/CNT/PEDOT on a GCE template (Fig. 5A). Finally, ultrapure water was used to

537

wash the modified electrode, and the electrode was left to dry in ambient conditions. The

538

characterization of NiO/CNT/PEDOT composite-modified electrode was carried out by SEM,

539

TEM, Raman spectra, and FTIR spectra (Fig. 5B and 5C). The response of the

540

NiO/CNT/PEDOT/GCE electrochemical sensor was then measured by CV, EIS, and DPV. The

541

linear responses for DA, 5-HT, and Trp were 0.03–20, 0.3–35, and 1–41 µM (LODs of 0.026,

542

0.063, and 0.210 µM), respectively.

AC C

EP

TE D

533

543

A cobalt (II) complex–based electrochemical sensor was deployed to detect DA in the presence

544

of AA and UA [163]. This sensor was synthesized by combining [(Co(bdmpzm)2(NCS)2] (bdmpzm

545

= bis(3,5-dimethylpyrazol-1-yl)methane) with SWCNT and Nafion. The material was then used to

546

modify a screen-printed carbon electrode (SPCE). The resulting sensor (Nafion-SWCNT24

ACCEPTED MANUSCRIPT [Co(bdmpzm)2(NCS)2]/SPCE) was evaluated for the oxidation of DA, with corresponding anodic

548

and cathodic peaks detected at 0.42 V and 0.29 V, respectively. The LOD for DA was 0.095 µM

549

[163]. Lete et al [164]. developed a boron-doped diamond microelectrode array (BDD-MEA) to

550

detect DA and AA. The BDD/MEA-based sensor showed a linear response for DA and AA

551

between 0.2 and 1 µM and between 20 and 200 µM, respectively.

RI PT

547

GO decorated with AuNPs has been used as an electrochemical sensor to simultaneously assess

553

UA and AA in urine samples [165]. In that sensor, GO doped with AuNPs was deposited over a

554

gold interdigitated microelectrode array (Au-IDA) to obtain the desired electrode design (AuNP-

555

GO/Au-IDA). The sensor electrodes were thoroughly characterized using field-emission scanning

556

electron microscopes (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron

557

spectroscopy (XPS), and CV. The electrochemical sensor, when tested for AA and UA, yielded

558

LODs of 1.4 (range, 4.6 to 193 µM) and 0.62 µM (range, 2 to 1050 µM), respectively [165].

M AN U

SC

552

560

TE D

559

4. Performance comparison between different sensing methods It is well established that electrochemical sensors are cost effective, efficient, and simple to use

562

in analytical methods because of their ease of miniaturization, detection sensitivity, and

563

reproducibility of results. The electrical/thermal conductivity and mechanical strength of CNTs and

564

graphene give them some merits over other NMs. CNTs, graphene, GO, and RGO have been used

565

extensively in constructing electrodes for NC sensing. Table 2 summarizes a few of the relevant

566

research studies. An electrochemical sensor based on CNTs exhibited an LOD of 2.3 10-6 µM, and

567

electrochemical sensors based on graphene exhibited an LOD of 3.6 10-3 µM, making them less

568

sensitive than the CNT-based sensor. Thus, CNTs could work as advanced electrode material in

569

sensing interfaces to detect NCs in biological samples.

AC C

EP

561

25

ACCEPTED MANUSCRIPT Currently, metallic NPs have gained significant consideration in the fabrication of

571

electrochemical sensors due to their inherent advantages, such as porosity and high-surface area.

572

Electrodes made from metallic NPs thus offer excellent electrochemical catalytic oxidation of NCs.

573

A linear range and LODs of 10-4–1.0 and 5x10-5 µM (Table 3) were achieved using metallic NPs

574

and the DPV technique, respectively. MIP-based electrochemical sensors have advantages such as

575

high selectivity and sensitivity, chemical/mechanical stability, reusability, facile preparation, low

576

cost, miniaturization, and automation. An electrochemical sensor based on MIPs exhibited a good

577

linear range of 2x10-7– 2x10-2 µM and an LOD of 6.83x10-8 µM using the CV technique (Table 3).

578

MIP-based electrochemical sensors have thus shown more sensitivity than electrochemical sensors

579

made with CNTs, metallic NPs, or graphene.

M AN U

SC

RI PT

570

580

Table 3 lists 17 electrochemical sensors based on MOFs, each of which has its own unique

581

composition and structure: G-ZIF8, Fe-MIL-88-H2O2-OPD, POMOF/RGO, RGO/ZIF8, Zr-

582

Porphyrin-MOF/MPC, Nafion/C/AL-MIL-53-(OH)2, Fe-MIL-88MOFs, Abtz-CdI2-MOF, Mn-

583

MOF/MWCT,

584

PMo10V2@MIL-101 (Cr), Luminol-H2O2-HKUST-1, ZnO@ZIF8, and Cu-hemin MOF/CS-RGO.

585

All those sensors exhibit good reproducibility of results, high sensitivity, good stability, a low LOD,

586

and a wide linear range for measuring NCs in serum, urine, plasma, serous buffer solution, or

587

hydrochloride injection. The ECL technique yielded a linear range of 1x10-6–1x10-2 µM and an

588

LOD of 2.9 x10-7 µM. In other words, electrochemical sensors based on MOFs are efficient

589

immobilization matrices. Additionally, the distinctive features of MOFs and their composites make

590

them optimal for constructing a wide range of sensing interfaces to extend the applications of

591

electrochemical sensors. Recent research shows that MOFs have applications in diverse fields,

592

including biomedical applications in which they can act as new therapeutic or diagnostic materials.

GNe-Cu-MOF,

UiO-66-NO2@XC-72,

Fe3O4@ZIF-8/RGO,

AC C

EP

TE D

MIL-101,

593

26

ACCEPTED MANUSCRIPT 594 5. Conclusion and outlook 595 Advancements in nanotechnology are associated with the emergence of various advanced functional

NMs, including CNTs, graphene, MIPs, MOFs, metals, and metal oxides. The potency of those

597

materials has been investigated in a wide variety of clinical analysis systems. Due to their many

598

useful properties (e.g., high surface area, good to excellent conductivity ranges, biocompatibility),

599

many NMs have been studied for the development of highly efficient electrochemical sensors,

600

making NM-based electrochemical sensing an exciting area for the analysis of NCs in different

601

biological samples (urine, serum, and tissue). In this review article, we discussed the most significant

602

achievements made in the field of NM-based electrochemical sensors for quantitative detection of

603

NCs and summarized the performance of those electrochemical sensors in relation to the type of NM.

604

NM-based electrochemical sensors for detecting NCs in biological fluids clearly have a bright and

605

exciting future. MOFs and MIPs are currently attracting the most interest due to their excellent

606

selectivity and specificity.

SC

M AN U

607

RI PT

596

Despite many known advantages of electrochemical sensing, its actual application toward NCs in

608 biological fluids faces several challenges in terms of (1) multiple target analysis with high 609 spatiotemporal resolution in real-time continuous monitoring, (2) long-term stability of the sensing

TE D

610 materials without device failure, (3) lower LODs with high sensitivity, selectivity, and reproducibility 611 for the target neurotransmitter in biological fluids, (4) fouling issues due to the adherence or 612 adsorption

of

the

proteins

in

real

613 samples, (5) lack of information on the toxicity of NMs, (6) recognition for the interactions between

EP

614 most NMs and the immune systems. The aforementioned challenges encountered in the deployment 615 of electrochemical sensors can be resolved by (1) the modifications in substrate material and

AC C

616 geometry using advanced nanoscale fabrication and machining techniques, (2) the introduction of 617 nanostructures with high surface-area-to-volume ratio, (3) incorporation of specific catalysts into the 618 sensor to increase its analytical performance by enhancing the rate of a particular chemical reaction, 619 and (4) development of electrode surfaces resistant to bio-fouling. Further developments in 620 electrochemical sensors by adopting above mentioned modifications, the electrochemical detection of 621 NCs might have great potential to revolutionize diagnosis and treatment of many neurological and 622 psychiatric disorders. 623 624

Acknowledgements 27


This study was supported by a grant from the National Research Foundation of Korea (NRF)

626

funded by the Ministry of Science, ICT, & Future Planning (Grant No: 2016R1E1A1A01940995).

627 628 References

[1]

study of the central nervous system, Prog. Neurobiol. 123 (2014) 18–36.

630 631

A. Ajetunmobi, A. Prina-Mello, Y. Volkov, A. Corvin, D. Tropea, Nanotechnologies for the

RI PT

629

[2]

S. Liang, J. Huang, W. Liu, H., Jin, L. Li, X. Zhang B. Nie, R. Lin, J. Tao, S. Zhao, B. Shan, L. Chen, Magnetic resonance spectroscopy analysis of neurochemical changes in the

633

atrophic hippocampus of APP/PS1 transgenic mice, Behav. Brain Res. 335 (2017) 26–31. [3]

J.S.A. Devi, S. Salini, A.H. Anulekshmi, G.L. Praveen, G. Son, Fe (III) ion modulated l-

M AN U

634

SC

632

635

DOPA protected gold nanocluster probe forfluorescence turn on sensing of ascorbic acid,

636

Sens. Actuators B 246 (2017) 943–951.

637

[4]

J.A. Ribeiro, P.M.V. Fernandes, C.M. Pereira, F. Silva, Electrochemical sensors and biosensors for determination of catecholamine neurotransmitters: A review, Talanta 160

639

(2016) 653–679.

640

[5]

TE D

638

S.K. Vashist, D. Zheng, K. Al-Rubeaan, J.H.T. Luong, F.S. Sheu, Advances in carbon nanotube based electrochemical sensors for bioanalytical applications, Biotechnol. Adv. 29

642

(2011) 169–188.

643

[6]

EP

641

W. Lee, N.H. Park, T.-B. Ahnb, B.C. Chung, J. Hong, Profiling of a wide range of neurochemicals in human urine by very-high-performance liquid chromatography-tandem

645

mass spectrometry combined with in situ selective derivatization, J. Chromatogr. A 1526 (2017) 47–57.

646 647

[7]

J. Xu, Y. Wang, S. Hu, Nanocomposites of graphene and graphene oxides: Synthesis,

molecular functionalization and application in electrochemical sensors and biosensors. A

648

review, Microchim. Acta 184 (2017) 1–44.

649 650

AC C

644

[8]

M. Raj, P. Gupta, R.N. Goyal, Y.B. Shim, Graphene/conducting polymer nano-composite

651

loaded screen printed carbon sensor for simultaneous determination of dopamine and 5-

652

hydroxytryptamine, Sens. Actuators B Chem. 239 (2017) 993–1002. 28


[9]

H. Song, G. Xue, J. Zhang, G. Wang, B.C. Ye, S. Sun, L. Tian, Y. Li, Simultaneous

654

voltammetric determination of dopamine and uric acid using carbon-encapsulated hollow

655

Fe3O4 nanoparticles anchored to an electrode modified with nanosheets of reduced graphene

656

oxide, Microchim. Acta 184 (2017) 843–853.

657

[10]

L. Jia, Y. Zhou, Y. Jiang, A. Zhang, X. Li, C. Wang, A novel dopamine sensor based on Mo doped reduced graphene oxide/polyimide composite membrane, J. Alloys Compd. 685

659

(2016) 167–174.

660

[11]

RI PT

658

D. Sun, H. Li, M. Li, C. Li, H. Dai, D. Sun, B. Yang, Electrodeposition synthesis of a NiO/CNT/PEDOT composite forsimultaneous detection of dopamine, serotonin, and

662

tryptophan, Sens. Actuators B 259 (2018) 433–442. [12]

basedelectrochemical sensors for biomolecules, ACS Nano 10 (2016) 46−80.

664 665

J.N. Tiwari, V. Vij, K.C. Kemp, K.S. Kim, Engineered carbon-nanomaterial-

M AN U

663

SC

661

[13]

C. Tan, G. Dutta, H. Yin, S. Siddiqui, P.U. Arumugam, Detection of neurochemicals with

666

enhanced

667

ultrananocrystalline diamond microelectrodes, Sens.Actuators B 258 (2018) 193–203. [14]

selectivity

via

hybrid

multiwall

carbon

nanotube-

B. Si, E. Song, Molecularly imprinted polymers for the selective detection of multi-analyte neurotransmitters, Microelectron. Eng. 187–188 (2018) 58–65.

669 670

and

TE D

668

sensitivity

[15]

H.H. Li, H.H. Wang, W.T. Li, X.X. Fang, X.C. Guo, W.H. Zhou, X. Cao, D.X. Kou, Z.J. Zhou, S.X. Wu, A novel electrochemical sensor for epinephrine based on three dimensional

672

molecularly imprinted polymer arrays, Sens. Actuators B Chem. 222 (2016) 1127–1133. [16]

imprinted electrochemical sensor for the point-of-care detection of a breast cancer

674

biomarker (CA 15-3), Sens. Actuators B 256 (2018) 905–912.

675 676

[17]

P. Yáñez-Sedeño, S. Campuzano, J.M. Pingarrón, Electrochemical sensors based on magnetic molecularly imprinted polymers: A review, Anal. Chim. Acta 960 (2017) 1–17.

677 678

J.G. Pacheco, M.S.V. Silva, M. Freitas, H.P.A. Nouws, C. Delerue-Matos, Molecularly

AC C

673

EP

671

[18]

H. Hosseini, H. Ahmar, A. Dehghani, A. Bagheri, A.Tadjarodi, A.R. Fakhari, A novel

679

electrochemical sensor based on metal–organic framework for electrocatalytic oxidation of

680

L-cysteine, Biosens. Bioelectron. 42 (2013) 426–429. 29


[19]

carbon composites for electrocatalytic applications, Electrochim. Acta 247 (2017) 41–49.

682 683

D. Yin, J. Liu, X. Bo, M. Li, L. Guo, Porphyrinic metal-organic framework/macroporous

[20]

C. Zhao, Z. Jiang, R. Mu, Y. Li, A novel sensor for dopamine based on the turn-on fluorescence

685

phenylenediamine system, Talanta 159 (2016) 365–370.

686

[21]

of

Fe-MIL-88

metal-organic

Renault,

688

electrochemical

689

ChemPlusChem 82 (2017) 561 – 569.

R. Sandulescu, C. Cristea, Detection of dopamine by a biomimetic sensor

based

on

polythioaniline-bridged

gold

nanoparticles,

SC

[22]

peroxide–o-

M.Tertis, A. Florea, A. Adumitrachioaie, A. Cernat, D. Bogdan, L. Barbu-Tudoran, N.J.

687

690

frameworks–hydrogen

RI PT

684

H.H. Wang, X.J. Chen, W.T. Li, W.H. Zhou, X.C. Guo, W.Y. Kang, D.X. Kou, Z.J. Zhou, Y.-N. Meng, Q.W.Tian, S.X., Wu, ZnO nanotubes supported molecularly imprinted

692

polymers arrays as sensing materials for electrochemical detection of dopamine, Talanta 176

693

(2018) 573–581.

694

[23]

M AN U

691

Y. Xin, Z. Li, W. Wu, B. Fu, H. Wu, Z. Zhang, Recognition unit-free and self-cleaning photoelectrochemical sensing platform on TiO2 nanotube photonic crystals for sensitive and

696

selective detection of dopamine release from mouse brain, Biosens. Bioelectron. 87 (2017)

697

396–403.

698

[24]

TE D

695

J. Li, H. Hu, H. Li, C. Yao, Recent developments in electrochemical sensors based on nanomaterials for determining glucose and its byproduct H2O2, J. Mater. Sci. 52 (2017)

700

10455-10469. [25]

organic framework composites as electrocatalysts for electrochemical sensing applications,

702

Coord. Chem. Rev. 357 (2018) 105–129.

703 704

[26]

[27]

709

R. Zhang, W. Chen, Recent advances in graphene-based nanomaterials for fabricating electrochemical hydrogen peroxide sensors, Biosens. Bioelectron. 89 (2017) 249-268.

707 708

C.Yang, M.E. Denno, P. Pyakurel, B.J. Venton, Recent trends in carbon nanomaterial-based electrochemical sensors for biomolecules: A review, Anal. Chim. Acta 887 (2015) 17–37.

705 706

S. Kempahanumakkagari, K. Vellingiri, A. Deep, E.E. Kwond, N. Bolan, K.H. Kim, Metal–

AC C

701

EP

699

[28]

G.A. Rivas, M.C. Rodríguez, M.D. Rubianes, F.A. Gutierrez, M. Eguílaz, P.R. Dalmasso, E.N. Primo, C. Tettamanti, M.L. Ramírez, A. Montemerlo, P. Gallay, C. Parrado, Carbon 30


nanotubes-based electrochemical (bio)sensors for biomarkers, Appl. Mater. Today 9 (2017)

711

566–588. [29]

detection of small molecule metabolites, Biotechnol. Adv. 34 (2016) 234–249.

713 714

F. Xiao, L. Wang, H. Duan, Nanomaterial based electrochemical sensors for in vitro

[30]

G. Maduraiveerana, M. Sasidharana, V. Ganesan, Electrochemical sensor and biosensor

RI PT

712

715

platforms based on advanced nanomaterials for biological and biomedical applications,

716

Biosens. Bioelectron. 103 (2018) 113–129. [31]

communication in the brain, Chem. Rev. 108 (2008) 2554–2584.

718 719

D.L. Robinson, A. Hermans, A.T. Seipel, R.M. Wightman, Monitoring rapid chemical

[32]

SC

717

F. Wu, P. Yu, L. Mao, Self-powered electrochemical systems as neurochemical sensors: toward self-triggered in vivo analysis of brain chemistry, Chem. Soc. Rev. 46 (2017) 2692–

721

2704.

722

[33]

M AN U

720

Z. Kazmi, I. Fatima, S. Perveen, S.S. Malik, Monosodium glutamate: Review on clinical reports, Int. J. Food Prop. 20:sup2 (2017) 1807-1815.

723

[34]

K. Kompoliti, L. Verhagen, Encyclopedia of Movement Disorders, Academic Press 2010.

725

[35]

J.M. Feldman, Serotonin. Encyclopedia of Gastroenterology, Three-Volume Set (2004) 346–351.

726

[36]

K. Vikrant, D.C. Tsang, N. Raza, B.S. Giri, D. Kukkar, K.-H. Kim, Potential utility of

EP

727

TE D

724

metal–organic framework-based platform for sensing pesticides, ACS Appl. Mater.

729

Interfaces 10 (2018) 8797–8817.

730

[37]

[38]

735

E. Bakker, M. Telting-Diaz, Electrochemical sensors,

Anal. Chem. 74 (2002) 2781–

2800.

733 734

B. Si, E. Song, Recent Advances in the detection of neurotransmitters, Chemosensors, 6 (2018) 1–24.

731 732

AC C

728

[39]

F. Faridbod, V.K. Gupta, H.A. Zamani, Electrochemical sensors and biosensors, int. j. electrochem. 2011 (2011).

31


[40]

I. Pantic, J. Paunovic, I. Dimitrijevic, A. Błachnio, A. Przepiorka, S. Pantic, Novel strategies

737

for neurotransmitter detection and measurement using advanced materials, Rev. Adv. Mater.

738

Sci. 42 (2015) 1–5.

739

[41]

P.K. Aneesh, S.R. Nambiar, T.P. Rao, A. Ajayaghosh, Electrochemically synthesized partially reduced graphene oxide modified glassy carbon electrode for individual and

741

simultaneous voltammetric determination of ascorbic acid, dopamine and uric acid, Anal.

742

Methods 6 (2014) 5322–5330.

743

[42]

RI PT

740

J. Li, Y. Wang, Y. Sun, C. Ding, Y. Lin, W. Sun, C. Luo, A novel ionic liquid functionalized graphene oxide supported gold nanoparticle composite film for sensitive

745

electrochemical detection of dopamine, RSC Adv. 7 (2017) 2315–2322. [43]

R. Li, T. Yang, Z. Li, Z. Gu, G. Wang, J. Liu, Synthesis of palladium@gold

747

nanoalloys/nitrogen

748

electrochemical detection of dopamine, Anal. Chim. Acta 954 (2017) 43–51.

749

[44]

and

M AN U

746

SC

744

sulphur-functionalized

multiple

graphene

aerogel

for

S.K. Kim, D. Kim, S. Jeon, Determination of dopamine in the presence of ascorbic acid by poly(styrene sulfonic acid) sodium salt/single-wall carbon nanotube film modified glassy

751

carbon electrode, Sens. Actuators B Chem. 174 (2012) 285–291.

752

[45]

TE D

750

N.K. Sadanandhan, M. Cheriyathuchenaaramvalli, S.J. Devaki, A.R.R. Menon, PEDOTreduced graphene oxide-silver hybrid nanocomposite modified transducer for the detection

754

of serotonin, J. Electroanal. Chem. 794 (2017) 244–253.

755

[46]

EP

753

C. Deng, J. Chen, M. Yang, Z. Nie, S. Si, Electrochemical determination of dopamine in the presence of ascorbic acid based on the gold nanorods/carbon nanotubes composite film,

757

Electrochim. Acta 56 (2011) 8851–8856.

758

[47]

T.Thomas, R.J. Mascarenhas, B.E.K. Swamy, P. Martis, Z. Mekhalif, B.S. Sherigara, Multiwalled carbon nanotube/poly(glycine) modified carbon paste electrode for the determination

759

of dopamine in biological fluids and pharmaceuticals, Colloids Surf B Biointerfaces 110

760

(2013) 458–465.

761 762

AC C

756

[48]

A.A. Ensafi, B. Arashpour, B. Rezaei, A.R. Allafchian, Voltammetric behavior of dopamine

763

at a glassy carbon electrode modified with NiFe2O4 magnetic nanoparticles decorated with

764

multiwall carbon nanotubes, Mater. Sci. Eng. C 39 (2014) 78–85. 32


[49]

M. Satyanarayana, K.K. Reddy, K.V. Gobi, Nanobiocomposite Based Electrochemical

766

Sensor for Sensitive Determination of Serotonin in Presence of Dopamine, Ascorbic Acid

767

and Uric Acid In Vitro, Electroanalysis 26 (2014) 2365–2372.

768

[50]

I. Cesarino, H.V. Galesco, S.A.S. Machado, Determination of serotonin on platinum electrode modified with carbon nanotubes/polypyrrole/silver nanoparticles nanohybrid,

770

Mater. Sci. Eng. C 40 (2014) 49–54.

771

[51]

RI PT

769

O.E. Fayemi, A.S. Adekunle, E.E. Ebenso, Electrochemical determination of serotonin in urine samples based on metal oxide nanoparticles/MWCNT on modified glassy carbon

773

electrode, Sens. Bio-Sensing Res. 13 (2017) 17–27.

774

[52]

SC

772

K. Kahlouche, R. Jijie, I. Hosu, A. Barras, T. Gharbi, R. Yahiaoui, G. Herlem, M. Ferhat, S. Szunerits, R. Boukherroub, Controlled modification of electrochemical microsystems with

776

polyethylenimine/reduced graphene oxide using electrophoretic deposition: Sensing of

777

dopamine levels in meat samples, Talanta 178 (2018) 432–440.

778

[53]

M AN U

775

S. Pruneanu, A.R. Biris, F. Pogacean, C. Socaci, M. Coros, M.C. Rosu, F. Watanabe, A.S. Biris, The influence of uric and ascorbic acid on the electrochemical detection of dopamine

780

using graphene-modified electrodes, Electrochim. Acta 154 (2015) 197–204.

781

[54]

TE D

779

H. Xu, J. Xiao, L. Yan, L. Zhu, B. Liu, An electrochemical sensor for selective detection of dopamine based on nickel tetrasulfonated phthalocyanine functionalized nitrogen-doped

783

graphene nanocomposites, J. Electroanal. Chem. 779 (2016) 92–98.

784

[55]

EP

782

I.M. Taylor, E.M. Robbins, K.A. Catt, P.A. Cody, C.L. Happe, X.T. Cui, Enhanced dopamine detection sensitivity by PEDOT/graphene oxide coating on in vivo carbon fiber

786

electrodes, Biosens. Bioelectron. 89 (2017) 400–410.

787

[56]

M. Cheng, X. Zhang, M. Wang, H. Huang, J. Ma, facile electrochemical sensor based on well-dispersed graphene-molybdenum disulfide modified electrode for highly sensitive

788

detection of dopamine, J. Electroanal. Chem. 786 (2017) 1–7.

789 790

AC C

785

[57]

L. Zhao, H. Li, S. Gao, M. Li, S. Xu, C. Li, W. Guo, C. Qu, B. Yang, MgO nanobelt-

791

modified graphene-tantalum wire electrode for the simultaneous determination of ascorbic

792

acid, dopamine and uric acid, Electrochim. Acta 168 (2015) 191–198.

33


[58]

W.L. Liu, C. Li, L. Tang, Y. Gu, Z.Q. Zhang, Facile Synthesis of Graphene-poly(styrene

794

sulfonate)-Pt Nanocomposite and Its Application in Amperometric Determination of

795

Dopamine, Chinese J. Anal. Chem. 41 (2013) 714–718.

796

[59]

Y.R. Kim, S. Bong, Y.J. Kang, Y. Yang, R.K. Mahajan, J.S. Kim, H. Kim, Electrochemical detection of dopamine in the presence of ascorbic acid using graphene modified electrodes,

798

Biosens. Bioelectron. 25 (2010) 2366–2369.

799

[60]

RI PT

797

N. Baig, A.N. Kawde, A cost-effective disposable graphene-modified electrode decorated with alternating layers of Au NPs for the simultaneous detection of dopamine and uric acid

801

in human urine, RSC Adv. 6 (2016) 80756–80765.

802

[61]

SC

800

D.B. Gorle and M.A. Kulandainathan, Electrochemical sensing of dopamine at the surface of a dopamine grafted graphene oxide/poly(methylene blue) composite modified electrode,

804

RSC Adv. 6 (2016) 19982–19991.

805

[62]

M AN U

803

H. Beitollahi, F.G. Nejad, S. Shakeri, GO/Fe3O4 @SiO2 core–shell nanocomposite-modified

806

graphite screen-printed electrode for sensitive and selective electrochemical sensing of

807

dopamine and uric acid, Anal. Methods 9 (2017) 5541–5549. [63]

F.H. Cincotto, T.C. Canevari, A.M. Campos, R. Landers, S.A.S. Machado, Simultaneous

TE D

808

determination of epinephrine and dopamine by electrochemical reduction on the hybrid

810

material SiO2/graphene oxide decorated with Ag nanoparticles, Analyst 139 (2014) 4634–

811

4640.

812

[64]

EP

809

X. Dong, Y. Ma, G. Zhu, Y. Huang, J. Wang, M.B. Chan-Park, L. Wang, W. Huang, P. Chen, Synthesis of graphene–carbon nanotube hybrid foam and its use as a novel three-

814

dimensional electrode for electrochemical sensing, J. Mater. Chem. 22 (2012) 17044 – 17048.

815 816

[65]

T. Kokulnathan, A.J. Anthuvan, S.M. Chen, V. Chinnuswamy, K. Kadirvelu, Trace level electrochemical determination of neurotransmitter dopamine in biological samples based on

817

iron oxide nanoparticles decorated graphene sheets, Inorg. Chem. Front. 5 (2018) 705–718.

818 819

AC C

813

[66]

P. Ekabutr, W. Klinkajon, P. Sangsanoh, O. Chailapakul, P. Niamlang, T. Khampieng, P.

820

Supaphol, Electrospinning: A Carbonized Gold/Graphene/PAN Nanofiber for High

821

Performance Biosensing, Anal. Methods 10 (2018) 874–883. 34


[67]

Q.M. Feng, M. Cai, C.G. Shi, N. Bao, H.Y. Gu, Integrated paper-based electroanalytical

823

devices for determination of dopamine extracted from striatum of rat, Sens. Actuators B

824

Chem. 209 (2015) 870–876. [68]

dopamine sensing, Electrochim. Acta 123 (2014) 362–368.

826 827

M. Amiri, H. Eynaki, Y. Mansoori, Cysteine-anchored receptor on carbon nanoparticles for

[69]

RI PT

825

M. Mazloum-Ardakani, A. Khoshroo, Electrocatalytic properties of functionalized carbon

828

nanotubes with titanium dioxide and benzofuran derivative/ionic liquid for simultaneous

829

determination of isoproterenol and serotonin, Electrochim. Acta 130 (2014) 634–641. [70]

I. Suzuki, M. Fukuda, K. Shirakawa, H. Jiko, M. Gotoh, Carbon nanotube multi-electrode

SC

830

array chips for noninvasive real-time measurement of dopamine, action potentials, and

832

postsynaptic potentials, Biosens. Bioelectron. 49 (2013) 270–275.

833

[71]

M AN U

831

B. Zhang, D. Huang, X. Xu, G. Alemu, Y. Zhang, F. Zhan, Y. Shen, M. Wang,

834

Simultaneous electrochemical determination of ascorbic acid, dopamine and uric acid with

835

helical carbon nanotubes, Electrochim. Acta 91 (2013) 261–266.

836

[72]

D. Patrascu, I. David, V. David, C. Mihailciuc, I. Stamatin, J. Ciurea, L. Nagy, G. Nagy, A.A., Ciucu, Selective voltammetric determination of electroactive neuromodulating species

838

in biological samples using iron (II) phthalocyanine modified multi-wall carbon nanotubes

839

paste electrode, Sens. Actuators B Chem. 156 (2011) 731–736. [73]

P.Y. Chen, R. Vittal, P.C. Nien, K.C. Ho, Enhancing dopamine detection using a glassy

EP

840

TE D

837

carbon electrode modified with MWCNTs, quercetin, and Nafion®, Biosens. Bioelectron.

842

24 (2009) 3504–3509.

843

[74]

Y. Zhang, Y. Cai, S. Su, Determination of dopamine in the presence of ascorbic acid by poly(styrene sulfonic acid) sodium salt/single-wall carbon nanotube film modified glassy

844

carbon electrode, Anal. Biochem. 350 (2006) 285291.

845 846

AC C

841

[75]

D. Thirumalai, D. Subramani, J.H. Yoon, J. Lee, H. Paik, S.C. Chang, De-–bundled single-

847

walled carbon nanotube-modified sensors for simultaneous differential pulse voltammetric

848

determination of ascorbic acid, dopamine, and uric acid, New J. Chem. 42 (2018) 2432–

849

2438.

35


[76]

S. Ali, R. Parajuli, Y. Balogun, Y. Ma, H. He, A Nonoxidative Electrochemical Sensor

851

Based on a Self-Doped Polyaniline/Carbon Nanotube Composite for Sensitive and Selective

852

Detection of the Neurotransmitter Dopamine: A Review, Sensors 8 (2008) 8423–8452.

853

[77]

X. Hun, S. Wang, S. Wang, J. Zhao, X. Luo, A photoelectrochemical sensor for ultrasensitive dopamine detection based on single-layer NanoMoS2modified gold electrode,

855

Sens. Actuators B Chem. 249 (2017) 83–89.

856

[78]

RI PT

854

Y. Oztekin, M. Tok, E. Bilici, L. Mikoliunaite, Z. Yazicigil, A. Ramanaviciene, A. Ramanavicius, Copper nanoparticle modified carbon electrode for determination of

858

dopamine, Electrochim. Acta 76 (2012) 201–207.

859

[79]

SC

857

R.P. Talemi, S.M. Mousavi, H. Afruzi, Using gold nanostars modified pencil graphite electrode as a novel substrate for design a sensitive and selective dopamine aptasensor,

861

Mater. Sci. Eng. C 73 (2017) 700–708.

862

[80]

J. Wu, F. Yin, Studies on the electrocatalytic oxidation of dopamine at phosphotungstic acid–ZnO spun fiber-modified electrode, Sens. Actuators B Chem. 185 (2013) 651–657.

863 864

M AN U

860

[81]

B. Rezaei, M.K. Boroujeni A.A. Ensafi, Fabrication of DNA, o-phenylenediamine, and gold nanoparticle bioimprinted polymer electrochemical sensor for the determination of

866

dopamine, Biosens. Bioelectron. 66 (2015) 490–496.

867

[82]

TE D

865

Y. Huang, C. Cheng, X. Tian, B. Zheng, Y. Li, H. Yuan, D. Xiao, M.M.F. Choi, Lowpotential amperometric detection of dopamine based on MnO2 nanowires/chitosan modified

869

gold electrode, Electrochim. Acta 89 (2013) 832–839. [83]

metal wires as microelectrode sensors for dopamine, Analyst 140 (2015) 7283–7292.

871 872

[84]

S. Reddy, B.E.K. Swamy, H.N. Vasan, H. Jayadevappa, ZnO and ZnO/polyglycine modified carbon paste electrode for electrochemical investigation of dopamine, Anal.

873

Methods 4 (2012) 2778–2783.

874 875

A.G. Zestos, C. Yang, C.B. Jacobs, D. Hensley, B.J. Venton, Carbon nanospikes grown on

AC C

870

EP

868

[85]

S. Mahshid, C. Li, S.S. Mahshid, M. Askari, A. Dolati, L. Yang, S. Luo, Q. Cai, Sensitive

876

determination of dopamine in the presence of uric acid and ascorbic acid using TiO2

877

nanotubes modified with Pd, Pt and Au nanoparticles, Analyst 136 (2011) 2322– 2329. 36


[86]

Z. Yang, X. Liu, Y. Wu, C. Zhang, Modification of carbon aerogel electrode with

879

molecularly imprinted polypyrrole for electrochemical determination of dopamine, Sens.

880

Actuators B Chem. 212 (2015) 457–463.

881

[87]

X. Gu, G. Jiang, G. Jiang, T. Chen, W. Zhan, X. Li, S. Wu, S. Tian, Detection of dopamine on a mercapto-terminated hexanuclear Fe(III) cluster modified gold electrode, Talanta 137

883

(2015) 189–196.

884

[88]

RI PT

882

G. Jiang, X. Gu, G. Jiang, T. Chen, W. Zhan, S. Tian, Application of a mercapto-terminated binuclear Cu(II) complex modified Au electrode to improve the sensitivity and selectivity

886

for dopamine detection, Sens. Actuators B Chem. 209 (2015) 122–130.

887

[89]

SC

885

M. Dervisevic, M. Senel, E. Cevik, Novel impedimetric dopamine biosensor based on boronic acid functional polythiophene modified electrodes, Mater. Sci. Eng. C 72 (2017)

889

641–649.

890

[90]

M AN U

888

Y. Li, H. Li, M. Li, C. Li, D. Sun, B.Yang, Porous boron-doped diamond electrode for

891

detection of dopamine and pyridoxine in human serum, Electrochim. Acta 258 (2017) 744–

892

753. [91]

D. Uzun, A.B. Gündüzalp, E. Hasdemir, Selective determination of dopamine in the

TE D

893

presence of uric acid and ascorbic acid by N,N′-bis(indole-3-carboxaldimine)-1,2-

895

diaminocyclohexane thin film modified glassy carbon electrode by differential pulse

896

voltammetry, J. Electroanal. Chem. 747 (2015) 68–76.

897

[92]

EP

894

Y. Wang, S. Hamid, X. Zhang, N. Akhtar, X. Zhang, T. He, An electrochemiluminescent biosensor for dopamine detection using a poly(luminol–benzidine sulfate) electrode

899

modified by tyramine oxidase, New J. Chem. 41 (2017) 1591–1597.

900

[93]

Y. Wu, Z. Dou, Y. Liu, G. Lv, T. Pu, X. He, Dopamine sensor development based on the modification of glassy carbon electrode with β-cyclodextrin-poly(N-isopropylacrylamide),

901

RSC Adv. 3 (2013) 12726– 12734.

902 903

AC C

898

[94]

T.R. Silva, I.C. Vieira, A biosensor based on gold nanoparticles stabilized in

904

poly(allylamine hydrochloride) and decorated with laccase for determination of dopamine,

905

Analyst 141 (2016) 216–224.

37


[95]

K. Liu, H. Pang, J. Zhang, H. Huang, Q. Liu, Y. Chu, Synthesis and characterization of a

907

highly stable poly (3,4-ethylenedioxythiophene)-gold nanoparticles composite film and its

908

application to electrochemical dopamine sensors, RSC Adv. 4 (2014) 8415–8420.

909

[96]

A.F. Khan, D.A.C. Brownson, E.P. Randviir, G.C. Smith, C.E. Banks, 2D Hexagonal Boron Nitride (2D-hBN) Explored for the Electrochemical Sensing of dopamine, Anal. Chem. 88

911

(2016) 9729–9737.

912

[97]

RI PT

910

C. Xue, X. Wang, W. Zhu, Q. Han, C. Zhu, J. Hong, X. Zhou, H. Jiang, Electrochemical serotonin sensing interface based on double-layered membrane of reduced graphene

914

oxide/polyaniline nanocomposites and molecularly imprinted polymers embedded with gold

915

nanoparticles, Sens. Actuators B Chem. 196 (2014) 57–63. [98]

H.S. Han, H.K. Lee, J. You, H. Jeong, S. Jeon, Electrochemical biosensor for simultaneous

M AN U

916

SC

913

917

determination of dopamine and serotonin based on electrochemically reduced GO-

918

porphyrin, Sens. Actuators B Chem. 190 (2014) 886–895.

919

[99]

T.D. Thanh, J. Balamurugan, H.V. Hien, N.H. Kim, J.H. Lee, A novel sensitive sensor for serotonin based on high-quality of AuAg nanoalloy encapsulated graphene electrocatalyst,

921


TE D

920

[100] H.S. Han, J. You, H. Jeong, S. Jeon, Synthesis of graphene oxide grafted poly(lactic acid)

923

with palladium nanoparticles and its application to serotonin sensing, Appl. Surf. Sci. 284

924

(2013) 438–445.

EP

922

[101] B. Dinesh, V. Veeramani, S.-M. Chen, R. Saraswathi, In situ electrochemical synthesis of

926

reduced graphene oxide-cobalt oxide nanocomposite modified electrode for selective

927

sensing of depression biomarker in the presence of ascorbic acid and dopamine, J.

928

AC C

925

Electroanal. Chem. 786 (2017) 169–176.

929

[102] A. Babaei, A.R.Taheri, M. Aminikhah, Nanomolar simultaneous determination of levodopa

930

and serotonin at a novel carbon ionic liquid electrode modified with Co(OH)2 nanoparticles

931 932 933

and multi-walled carbon nanotubes, Electrochim. Acta 90 (2013) 317–325. [103] Y. Wang, S. Wang, L. Tao, Q. Min, J. Xiang, Q. Wang, J. Xie, Y. Yue, S. Wu, X. Li, H. Ding,

A

disposable

electrochemical

38

sensor

for

simultaneous

determination

of

ACCEPTED MANUSCRIPT norepinephrine and serotonin in rat cerebrospinal fluid based on MWNTs-ZnO/chitosan

935

composites modified screen-printed electrode, Biosens. Bioelectron. 65 (2015) 31–38.

936

[104] M. Mazloum-Ardakani, A. Khoshroo, High sensitive sensor based on functionalized carbon

937

nanotube/ionic liquid nanocomposite for simultaneous determination of norepinephrine and

938

serotonin, J. Electroanal. Chem. 717–718 (2014) 17–23.

RI PT

934

939

[105] A. Babaei, A.R. Taheri, Nafion/Ni(OH)2 nanoparticles-carbon nanotube composite modified

940

glassy carbon electrode as a sensor for simultaneous determination of dopamine and

941

serotonin in the presence of ascorbic acid, Sensors Actuators B Chem. 176 (2013) 543–551. [106] E. Rand, A. Periyakaruppan, Z. Tanaka, D.A. Zhang, M.P. Marsh, R.J. Andrews, K.H. Lee,

943

B. Chen, M. Meyyappan, J.E. Koehne, A carbon nanofiber based biosensor for simultaneous

944

detection of dopamine and serotonin in the presence of ascorbic acid, Biosens. Bioelectron.

945

42 (2013) 434–438.

M AN U

SC

942

946

[107] A.G. Güell, K.E. Meadows, P.R. Unwin, J.V., Macpherson, Trace voltammetric detection of

947

serotonin at carbon electrodes: comparison of glassy carbon, boron doped diamond and

948

carbon nanotube network electrodes, Phys. Chem. Chem. Phys. 12 (2010) 10108– 10114. [108] M. Tertiș, A. Cernat, D. Lacatiș, A. Florea, D. Bogdan, M., Suciu, R. Săndulescu, C. Criste,

950

Highly selective electrochemical detection of serotonin on polypyrrole and gold

951

nanoparticles-based 3D architecture, Electrochem. Commun. 75 (2017) 43–47.

TE D

949

[109] A.C. Anithaa, K. Asokan, C. Sekar, Highly sensitive and selective serotonin sensor based on

953

gamma ray irradiated tungsten trioxide nanoparticles, Sensors Actuators B Chem. 238

954

(2017) 667–675.

AC C

EP

952

955

[110] X. Wei, F. Wang, Y. Yin, Q. Liu, L. Zou, B. Ye, Selective detection of neurotransmitter

956

serotonin by a gold nanoparticle-modified glassy carbon electrode, Analyst, 135 (2010)

957

2286– 2290.

958

[111] G. Ran, X. Chen, Y. Xia, Electrochemical detection of serotonin based on a

959

poly(bromocresol green) film and Fe3O4 nanoparticles in a chitosan matrix, RSC Adv. 7

960

(2017) 1847–1851.

39


[112] M.A. Mohamed, S.A. Atty, A.M. Yehia, C.W. Foster, C.E. Banks, N.K. Allam,

962

Electrochemical Determination of the Serotonin Reuptake Inhibitor, Dapoxetine, Using

963

Cesium–Gold Nanoparticles, ACS Omega 2 (2017) 6628–6635. [113] M. Song, S. Kim, N.K. Min, J. Jin, Electrochemical serotonin monitoring of

965

poly(ethylenedioxythiophene):poly(sodium 4-styrenesulfonate)-modified fluorine-doped tin

966

oxide by predeposition of self-assembled 4-pyridylporphyrin, Biosens. Bioelectron. 52

967

(2014) 411–416.

969

[114] F. Wang, Y. Wu, K. Lu, B. Ye, A simple but highly sensitive and selective calixarene-based voltammetric sensor for serotonin, Electrochim. Acta 87 (2013) 756–762.

SC

968

RI PT

964

[115] J. Wei, J.B. He, S.Q. Cao, Y.W. Zhu, Y. Wang, G.P. Hang, Enhanced sensing of ascorbic

971

acid, dopamine and serotonin at solid carbon paste electrode with a nonionic polymer film,

972

Talanta 83 (2010) 190–196.

M AN U

970

973

[116] A. Özcan, S. İlkbaş, Poly(pyrrole-3-carboxylic acid)-modified pencil graphite electrode for

974

the determination of serotonin in biological samples by adsorptive stripping voltammetry,

975

Sens. Actuators B Chem. 215 (2015) 518–524.

977

[117] P. Gupta, R.N. Goyal, . Polymelamine modified edge plane pyrolytic graphite sensor for the

TE D

976

electrochemical assay of serotonin, Talanta 120 (2014) 17–22. [118] M. Liu, J. Xiang, J. Zhou, H. Ding, A disposable amperometric sensor for rapid detection of

979

serotonin in the blood and brain of the depressed mice based on Nafion membrane-coated

980

colloidal gold screen-printed electrode, J. Electroanal. Chem. 640 (2010) 1–7.

982 983 984

[119] L. Liu, Y. Zhou, S. Liu, M. Xu, The applications of metal organic frameworks in

AC C

981

EP

978

electrochemical sensors, ChemElectroChem 5 (2018) 6–19.

[120] H.S. Wang, Metal–organic frameworks for biosensing and bioimaging applications, Coord. Chem. Rev. 349 (2017) 139–155.

985

[121] S. Achmann, G. Hagen, J. Kita, I.M. Malkowsky, C. Kiener, R. Moos, Metal–organic

986

frameworks for sensing applications in the gas phase, Sensors 9 (2009) 1574–1589.

40


[122] W.J. Ma, Q. Jiang, P. Yu, L.F. Yang, L.Q. Mao, Zeolitic imidazolate framework based

988

electrochemical biosensor for in vivo electrochemical measurements, Anal. Chem. 85

989

(2013) 7550–7557. [123] Y.Y. Zheng, C.X. Li, X.T. Ding, Q. Yang, YM. Qi, H.M. Zhang, L.T. Qu, Detection of

991

dopamine at graphene-ZIF-8 nanocomposite modified electrode, Chin. Chem. Lett. 28

992

(2017) 1473–1478.

RI PT

990

[124] G.Yu, J. Xia, F. Zhang, Z. Wang, Hierarchical and hybrid RGO/ZIF-8 nanocomposite as

994

electrochemical sensor for ultrasensitive determination of dopamine, J. Electroanal. Chem.

995

801 (2017) 496–502.

SC

993

[125] Y. Wang, H. Ge, G. Ye, H. Chen, X. Hu, Carbon functionalized metal organic

997

framework/Nafion composites as novel electrode materials for ultrasensitive determination

998

of dopamine, J. Mater. Chem.B 3 (2015) 3747–3753.

M AN U

996

[126] M. Nie, S. Lu, D. Lei, C. Yang, Z. Zhao, Rapid synthesis of ZIF-8 nanocrystals for

1000

Electrochemical detection of dopamine, J. Electrochem. Soc. 164 (2017) H952-H957.

1001

[127] X. Fu, Y. Yang, N. Wang, S. Chen, The electrochemiluminescence resonance energy

1002

transfer betweenFe-MIL-88 metal–organic framework and 3,4,9,10-perylenetetracar-boxylic

1003

acid for dopamine sensing, Sens. Actuators B 250 (2017) 584–590.

TE D

999

[128] Y. Cheng, J. Wu, C. Guo, X.G. Li, B. Ding, Y. Li, A facile water-stable MOF-based “off–

1005

on” fluorescent switch for label-free detection of dopamine in biological fluid, J. Mater.

1006

Chem. B 5 (2017) 2524–2535.

1008 1009

[129] M.Q. Wang, C.Ye, S.J. Bao, Y. Zhang, Y.N. Yu, M.W. Xu, Carbon nanotubes implanted

AC C

1007

EP

1004

manganese-based MOFs for simultaneous detection of biomolecules in body fluids, Analyst 141 (2016) 1279–1285.

1010

[130] Y. Li, C. Huangfu, H. Du, W. Liu, Y. Li, J. Ye, Electrochemical behavior of metal–organic

1011

framework MIL-101 modified carbon paste electrode: An excellent candidate for

1012

electroanalysis, J. Electroanal. Chem. 709 (2013) 65–69.

1013

[131] W. Zhang, J. Chen, Y. Li, W. Yang, Y. Zhang, Y. Zhang, Novel UIO-66-NO2@XC-72

1014

nanohybrid as an electrode material for simultaneous detection of ascorbic acid, dopamine

1015

and uric acid, RSC Adv. 7 (2017) 5628–5635. 41


[132] D.M. Fernandes, A.D.S. Barbosa, J. Pires, S.S. Balula, L. Cunha-Silva, C. Freire, Novel

1017

Composite Material Polyoxovanadate@MIL-101(Cr): A Highly Efficient Electrocatalyst for

1018

Ascorbic Acid Oxidation, ACS Appl. Mater. Interfaces 5 (2013) 13382–13390. [133] W. Zhang, G. Jia, Z. Li, C. Yuan, Y. Bai, D. Fu, Selective electrochemical detection of

1020

dopamine on polyoxometalate-based metal–organic framework and its composite with

1021

reduced graphene oxide, Adv. Mater. Interfaces 4 (2017) 1601241–1601248.

RI PT

1019

[134] J. Yang, F. Zhao, B. Zeng, One-step synthesis of a copper-based metal–organic framework–

1023

graphene nanocomposite with enhanced electrocatalytic activity, RSC Adv. 5 (2015)

1024

22060–22065.

SC

1022

[135] Y. Wang, Y. Zhang, C. Hou, M. Li, Magnetic Fe3O4@MOFs decorated graphene

1026

nanocomposites as novel electrochemical sensor for ultrasensitive detection of dopamine,

1027

RSC Adv. 5 (2015) 98260–98268.

M AN U

1025

[136] Q. Zhu, Y. Chen, W. Wang, H. Zhang, C. Ren, H. Chen, X. Chen, Q., Chen, Y., Wang, W.,

1029

Zhang, H., Ren, C., Chen, H., Chen, X., Sens. 2015. A sensitive biosensor for dopamine

1030

determination based on the unique catalytic chemiluminescence of metal–organic

1031

framework HKUST-1, Sens. Actuators B 210 (2015) 500–507.

1032

[137] W.W.

Zhan,

TE D

1028

Q.

Kuang,

J.Z.

Zhou,

Kong,

Xie,

L.S.

ZnO@ZIF-8 nanorods with selective photoelectrochemical response, J. Am. Chem. Soc.

1035

135 (2013) 1926–1933.

EP

1034

A case of

[138] L. Wang, H. Yang, J. He, Y. Zhang, J. Yu, Y. Song, Cu-hemin metal-organicframeworks/chitosan-reduced

AC C

1038

heterostructures:

Zheng,

Semiconductor@metal–organic

1037

core–shell

Z.X.

1033

1036

framework

X.J.

graphene oxide nanocomposites

with

peroxidase-like

bioactivity for electrochemical sensing, Electrochim. Acta 213 (2016) 691-697.

1039

[139] R. Gui, H. Jin, H. Guo, Z. Wang, Recent advances and future prospects in molecularly

1040

imprinted polymers-based electrochemical biosensors, Biosens. Bioelectron. 100 (2018) 56–

1041

70.

1042

[140] B. Li, Y. Zhou, W. Wu, M. Liu, S. Mei, W. Zhou, T. Jing, Highly selective and sensitive

1043

determination of dopamine by the novel molecularly imprinted poly(nicotinamide)/CuO

1044

nanoparticles modified electrode, Biosens. Bioelectron. 67 (2015) 121–128. 42


[141] M. Zhong, Y. Teng, S. Pang, L. Yan, X. Kan, Pyrrole–phenylboronic acid: A novel

1046

monomer for dopamine recognition and detection based on imprinted electrochemical

1047

sensor, Biosens. Bioelectron. 64 (2015) 212–218. [142] M. Porcel-Valenzuela, A. Salinas-Castillo, E. Morallón, F. Montilla, Molecularly imprinted

1049

silica films prepared by electroassisted deposition for the selective detection of dopamine,

1050

Sens. Actuators B 222 (2016) 63–70.

RI PT

1048

[143] J. Li, N. Zhang, Q. Sun, Z. Bai, J. Zheng, Electrochemical sensor for dopamine based on

1052

imprinted silica matrix-poly(anilineboronic acid) hybrid as recognition element, Talanta 159

1053

(2016) 379–386.

SC

1051

[144] M. Tertiș, A. Cernat, D. Lacatiș, A., Florea, D., Bogdan, M. Suciu, R. Săndulescu, C. Criste,

1055

Highly selective electrochemical detection of serotonin on polypyrrole and gold

1056

nanoparticles-based 3D architecture, Electrochem. Commun. 75 (2017) 43–47.

M AN U

1054

1057

[145] Y. Li, H. Song, L. Zhang, P. Zuo, B.-C. Ye, J. Yao, W. Chen, Support less electrochemical

1058

sensor based on molecularly imprinted polymer modified nanoporous microrod for

1059

determination of dopamine at trace level, Biosens. Bioelectron. 78 (2016) 308–314. [146] K. Saksena, A. Shrivastava, R. Kant, Chiral analysis of ascorbic acid in bovine serum using

1061

ultrathin molecular imprinted polyaniline/graphite electrode, J. Electroanal. Chem. 795

1062

(2017) 103–109.

TE D

1060

[147] Y. Teng, F. Liu, X. Kan, Voltammetric dopamine sensor based on three-dimensional

1064

electrosynthesized molecularly imprinted polymers and polypyrrole nanowires, Microchim.

1065

Acta 184 (2017) 2515–2522.

AC C

EP

1063

1066

[148] Y. Li, J. Liu, M. Liu, F. Yu, L. Zhang, H. Tang, B.C. Ye, L. Lai, Fabrication of ultra-

1067

sensitive and selective dopamine electrochemical sensor based on molecularly imprinted

1068 1069

polymer modified graphene@carbon nanotube foam, Electrochem. Commun. 64 (2016) 42– 45.

1070

[149] Y. Liu, J. Liu, J. Liu, W. Gan, B.C. Ye, Y. Li, Highly sensitive and selective voltammetric

1071

determination of dopamine using a gold electrode modified with a molecularly imprinted

1072

polymeric film immobilized on flaked hollow nickel nanospheres, Microchim. Acta 184

1073

(2017) 1285–1294. 43


[150] C.Yan, X. Liu, R. Zhang, Y. Chen, G. Wang, A selective strategy for determination of

1075

ascorbic acid based onmolecular imprinted copolymer of o-phenylenediamine and pyrrole, J.

1076

Electroanal. Chem. 780 (2016) 276–281. [151] X. Kan, H. Zhou, C. Li, A. Zhu, Z. Xing, Z. Zhao, Imprinted electrochemical sensor for

1078

dopamine recognition and determination based on a carbon nanotube/polypyrrole film,

1079

Electrochim. Acta 63 (2012) 69–75.

1080 1081

RI PT

1077

[152] W. Song, Y. Chen, J. Xu, X.R. Yang, D.B. Tian, Dopamine sensor based on molecularly imprinted electrosynthesized polymers, J. Solid State Electrochem. 14 (2010) 1909–1914. [153] D. Yu, Y. Zeng, Y. Qi, T. Zhou, G. Shi, A novel electrochemical sensor for determination of

1083

dopamine based on AuNPs@SiO2 core-shell imprinted composite, Biosens. Bioelectron. 38

1084

(2012) 270 –277.

1086

M AN U

1085

SC

1082

[154] W. Li, D. Qian, Y. Li, N. Bao, H. Gu, C. Yu, Fully-drawn pencil-on-paper sensors for electroanalysis of dopamine, J. Electroanal. Chem. 769 (2016) 72–79. [155] Y.B. Zeng, Y. Zhou, L. Kong, T.S. Zhou, G.Y. Shi, A novel composite of SiO2-coated

1088

graphene oxide and molecularly imprinted polymers for electrochemical sensing dopamine,

1089


TE D

1087

[156] M.K.L. Coelho, J.d.F. Giarola, A.T.M. da Silva, C.R.T. Tarley, K.B. Borges, A.C. Pereira,

1091

Development and application of electrochemical sensor based on molecularly imprinted

1092

polymer and carbon nanotubes for the determination of carvedilol, Chemosensors 4 (2016)

1093

22.

1095

[157] C. Zhu, G. Yang, H. Li, D. Du, Y. Lin, Electrochemical sensors and biosensors based on

AC C

1094

EP

1090

nanomaterials and nanostructures, Anal. Chem. 87 (2015) 230−249.

1096

[158] E. Mazzotta, A. Caroli, E. Primiceri, A.G. Monteduro, G. Maruccio, C. Malitesta, All-

1097

electrochemical approach for the assembly of platinum nanoparticles/polypyrrole nanowire

1098

composite with electrocatalytic effect on dopamine oxidation, J. Solid State Electrochem. 21

1099

(2017) 3495–3504.

1100

[159] S. Ramirez, N. Silva, M.P. Oyarzun, J. Pavez, J.F. Silva, Gold nanostructures on self-

1101

assembled monolayers activity for epinephrine, noradrenaline and dopamine, J. Electroanal.

1102

Chem. 799 (2017) 349–357. 44


[160] Y. Lin, K. Wang, Y. Xu, L. Li, J. Luo, C. Wang, Facile development of Au-ring

1104

microelectrode for in vivo analysis using non-toxic polydopamine as multifunctional

1105

material, Biosens. Bioelectron. 78 (2016) 274–280. [161] S. Mukdasai, U. Crowley, M. Pravda, X. He, E.P. Nesterenko, P.N. Nesterenko, B. Paull, S.

1107

Srijaranai, J.D. Glennon, E. Moore, Electrodeposition of palladium nanoparticles on porous

1108

graphitized carbon monolith modified carbon paste electrode for simultaneous enhanced

1109

determination of ascorbic acid and uric acid, Sens. Actuators B 218 (2015) 280–288.

1110

[162] S. Mukdasai, V. Langsi, M. Pravda, S. Srijaranaia, J.D. Glennon, A highly sensitive

1111

electrochemical determination of norepinephrineusing l-cysteine self-assembled monolayers

1112

over goldnanoparticles/multi-walled carbon nanotubes electrode in thepresence of sodium

1113

dodecyl sulfate, Sens. Actuators B 236 (2016) 126–135.

M AN U

SC

RI PT

1106

1114

[163] E. Nagles, L. Ibarra, J.P. Llanos, J. Hurtado, O. Garcia-Beltrán, Development of a novel

1115

electrochemical sensor based on cobalt(II) complex useful in the detection of dopamine in

1116

presence of ascorbic acid and uric acid, J. Electroanal. Chem. 788 (2017) 38–43.

1118

[164] C. Lete, F. Teodorescu, M. Marina, Determination of dopamine and ascorbic acid using boron doped diamond microelectrode arrays, Rev. Chim. 64 (2013) 540–544.

TE D

1117

[165] A. Abellán-Llobregat, L. Vidal, R. Rodríguez-Amaro, Á. Berenguer-Murcia, A. Canals E.

1120

Morallón, Au-IDA microelectrodes modified with Au-doped graphene oxide for the

1121

simultaneous determination of uric acid and ascorbic acid in urine samples, Electrochim.

1122

Acta 227 (2017) 275–284.

EP

1119

[166] O. Yasemin, T. Mutahire, B. Esra, M. Lina, Y. Zafer, R. Almira, R. Arunas, Copper

1124

nanoparticle modified carbon electrode for determination of dopamine, Electrochim. Acta

1125

AC C

1123

76 (2012) 201–207.

1126

[167] C. Xue, Q. Han, Y. Wang, J. Wu, T. Wen, R. Wang, J. Hong, X. Zhou, H. Jiang,

1127

Amperometric detection of dopamine in human serumby electrochemical sensor based on

1128

gold nanoparticles doped molecularly imprinted polymers, Biosens. Bioelectron. 49 (2013)

1129

199–203.

1130

[168] X. Liu, X.Y. Zhang L.L.Wang, Y.Y. Wang, A sensitive electrochemical sensor for

1131

paracetamol based on a glassy carbon electrode modified with multiwalled carbon 45


nanotubes and dopamine nanospheres functionalized with gold nanoparticles, Microchim.

1133

Acta 181 (2014) 1439–1446. [169] S. Govindaraju, S.R. Ankireddy, B. Viswanath, J. Kim, K. Yun, Fluorescent gold

1135

nanoclusters for selective detection of dopamine in cerebrospinal fluid, Scientific reports 7

1136

(2017) 402–411.

1138 1139 1140

[170] C. Xia, C. Xiaolan, W. Ning, Selective sensing of dopamine at MnOOH nanobelt modified electrode, Sens. Actuators B 160 (2011) 771– 776.

[171] A. Roychoudhury, S. Basu, S.K., Jha, Dopamine biosensor based on surface functionalized nano structured nickel oxide platform, Biosens. Bioelectron. 84 (2016) 72–81.

SC

1137

RI PT

1134

[172] R. Han, J. Ma, L. He, Development of an electrochemical sensor for catecholamine

1142

detection via a layer-by-layer fabrication method, Int. J. Electrochem. Sci. 12 (2017) 10338

1143

– 10347.

M AN U

1141

AC C

EP

TE D

1144

46

ACCEPTED MANUSCRIPT

Table 1 A list of neurochemicals and their physiochemical characteristics

Precursor

Location

146.2

C7H16NO2

Choline

Neuromuscular, CNS

2

Serotonin

176.21

C10H12N2 O

Tryptophan

Gut, CNS

3

Dopamine

153.17

C8H11NO2

L-DOPA, Tyrosine

Hypothalamus

4

Norepinephrine

169.17

C8H11NO3

Dopamine

Adrenal medulla

5

L-DOPA

197.18

C9H11NO4

6

Tryptophan

204.22

C11H12N2 O2

7

GABA

103.12

C4H9NO2

Tyrosine

AC C

Drugs that decrease or block

Receptor

Function

Nicotine, muscarine, Alzheimer drugs Cocaine, tricyclic antidepressents, psychedelics Cocaine, Parkinson’s drugs, amphetamines

Atropine, biperiden, scopolamine

Nicotinic, muscarinic

Excitatory, memory, muscle control, secretions, heart rate

Zofran, tryptophandepleted drinks Antipsychotics (Haldol) , reserpine

5-HT

Sleep, mood, intestinal movement control, muscle control Voluntary motion, reward pathways, cognition

D1, D2, D3, D4, D5 Adrenergic

Hypothalamus

Anthranilic acid

Blood

Glutamate

Brain

47

Drugs that increase or mimic

SC

A: Small molecules 1 Acetylcholine

Structure

M AN U

Mol. Formula

TE D

Mol. Wt. (g/mole)

EP

Neurochemical

RI PT

Order

Increased heart rate, increased oxygen to brain and muscles, increases happiness and alertness Treat Parkinson disorders

Nitrogen balance, proper growth Alcohol, barbiturates, baclofen, muscimol

Flumazenil, phaclofen

GABAA, GABAB

Inhibits CNS, increases sleepiness, decreases anxiety, alertness, and memory

ACCEPTED MANUSCRIPT

Glycine

75.06

C2H5NO2

DL-threonine

Spinal cord, brainstem

NMDA

Inhibits signals

9

Tyramine

137.17

C8H11NO

Tyrosine

CNS, kidney

TA1

Blood pressure regulation

10

Glutamate

145.11

C5H7NO4-

Non-essential amino acid

CNS, PNS

NMDA

2

Long term potentiation, memory

Testis, blood

Testosterone

288.42

C19H28O2

DHEA

12

Estrogen conjugated

372.41

C18H21Na O5S

13

Cortisol

362.46

C21H30O5

14

Epinephrine

183.20

C9H13NO3

Dehydroisoandrosterone sulfate Proopiomelanocortin Dopamine

15

Adenosine

267.24

C10H13N5 O4

16

Histamine

111.14

C5H9N3

1084.23

C46H65N15 O12S2

Ketamine, dextromethorphan

Maintain male sex characteristics related to hair follicles and skeletal muscle

M AN U

TE D

Placenta, blood

Adrenal cortex

Treat inflammation, allergy, asthma, shock

Adrenal medulla

Beta 1

A1, A2A, A2B

EP

ATP, AMP

Histidine

Opiates, betahistine

AC C

B: Neuropeptides 17 Vasopressin

Domoic acid, D-Cycloserine

SC

11

RI PT

8

Hypothalamus

48

Benadryl, Tagamet, Zantac

Adrenergic systems, stimulates heart, dilates bronchi and cerebral vessels Vasodilatory, analgesic, and antiarrhythmic Stimulant of gastric secretion, vasodilator, constrictor of bronchial muscles Antidiuretic hormone, regulates extracellular fluid volume, vasoconstrictor

ACCEPTED MANUSCRIPT

1007.19

C43H66N12 O12S2

Brain

20

Endorphin (beta)

3463

C158H253N 41O44S

Brain

21

Cholecystokinin

3931.45

C166H261N 51O52S4

Intestinal mucosa, CNS

22

Insulin

5831.64

C166H261N 51O52S4

C: Gasotransmitters 23 Nitric oxide

30

NO

Arginine

24

28

CO

Hemoglobin breakdown

Carbon monoxide

Uterine contraction, milk ejection

Analgesic

Contraction of gallbladder, drug tolerance, pain hypersensitivity

Pancreas

M AN U

Preproinsulin

OXTR

RI PT

Oxytocin

SC

19

Vascular endothelium

Vitamin C

Vasodilator, inhibits platelet aggregation

AC C

EP

TE D

Causes respiratory issues due to carboxyhemoglobin, anti-inflammatory, vasodilation 5-HT: 5-hydroxytrptamine; GABA: gamma aminobutyric acid; NMDA: N-methyl-d-aspartate; CNS: central nervous system; GABAB: gamma aminobutyric acid B; PNS: peripheral nervous system; L-DOPA: levodopa; DHEA: dehydroepiandrosterone; ATP: adenosine triphosphate; AMP: adenosine monophosphate; OXTR: oxytocin receptor

49

ACCEPTED MANUSCRIPT

Table 2 Nanomaterial-based electrochemical sensors for the detection of dopamine and serotonin Type of

S No

Method

Electrode & interface material

LOD

RI PT

material A] Dopamine

2

Graphene

DPV

AuE-RGO-polyethylenimine

DPV

50 nM

GCE - Pd@Gold nano alloys-N-S functionalized graphene aerogel

3.6×10

-10

[43]

2.05×10-7 M

[53] [54]

3

SWV

AuE - Gr-Au-Ag electrodes

4

Amperometry

N doped GR-Ni tetra sulfonated phthalocyanine

100 nM

5

CV

PEDOT-GO CFEs

0.085 µM -9

M AN U

[52]

M

SC

1

Ref.

[55] -1

6

DPV

GR-molybdenum disulfide hybrids

7.13×10 mol L

[56]

7

DPV

MgO nano-belt-modified graphene-tantalum

0.15 µM

[57]

4×10-8 M

[58]

[59]

wire electrode Amperometry

Graphene-poly(styrene sulfonate)-Pt

TE D

8

nanocomposite

DPV

GCE - graphene modified electrodes

2.64 µM

10

DPV

GR/Au/GR/Au/GPE

0.024 µM

EP

9

[60]

-6

-1

DPV

GCE - GO – poly methylene blue composite

1.03×10 mol L

[61]

12

DPV

SPCE – GO - Fe3O4 @ SiO2 core-shell

8.9×10-8 M

[62]

2.3 nM

[42]

13 14

DPV DPV

AC C

11

15

DPV

16

Amperometry

nanocomposite

GCE – GO – IL – Au NPs

GCE - reduced graphene oxide

-9

8×10 M

[41] -1

Ag NPs - SiO2 – GO - GCE

0.26 µmol L

[63]

GCE - 3D graphene–CNT hybrids

20 nM

[64]

50

ACCEPTED MANUSCRIPT

Amperometry

GCE – GR - Fe2O3 NPs

0.001 µM

[65]

18

DPV

SPCE - carbonized gold – graphene - PAN

0.8 NM

[66]

DPV

MWCNT - poly(glycine) modified CPE - glycine

1.2 × 10-8 M

[47]

DPV

ITO-MWCNT-Nafion-oxygen plasma treatment

0.01 µM

[67]

CNT

20 21

DPV

22

GCE - modified with NiFe2O4 - MWCNT

DPV

GCE - cysteine-anchored CNT

-1

3.6 × 10 mol L

CPE - MWCNT - PBD

24

Amperometry

ITO - CNT multi-electrode array

M AN U

DPV

DPV

0.02 µmol L -9

23

25

-1

SC

19

RI PT

17

GCE - poly(di allyl dimethyl ammonium

-1

1 µmol L 1 nM

[48] [68] [69] [70]

0.08 µM L

-1

[71]

chloride) @ helical CNTs 26

DPV

Fe (II) phthalocyanine MWCNT paste electrode

2.5 × 10-7 M

[72]

27

CV

GCE - CNT - gold nano rods

0.8 nM

[46] -1

Amperometry

GCE - MWCNT – quercetin - Nafion

1.4 µmol L

29

DPV

GCE – polystyrene sulfonic acid - SWCNT

8 × 10-9 M

[74]

30

DPV

GCE - De-bundled SWCNT

15 nM

[75]

31

CV

GCE – ssDNA – CNT - poly aniline - Nafion

1.5 nM

[76]

AuE – nano MoS2

2.3 × 10-12 M

[77]

GCE Cu NPs

50 pM

[78]

Metal &

PEC

33

metal

Amperometry

34

oxides

EIS

AC C

32

EP

TE D

28

Gold nanostars modified pencil graphite

-1

[73]

0.29 ng L

[79]

0.089 µM

[80]

6 nM

[81]

electrode (PGE)-Aptamer

35

36

DPV

DPV

Pt E - phosphotungstic acid - ZnO fiber-modified electrode

PGE - Au NPs – bio imprinted polymer

51

ACCEPTED MANUSCRIPT

37

Amperometry

Au E - MnO2 nanowires - chitosan

40 nM

[82]

38

CV

Carbon nano spikes on metal wires (Ta, Pd, Nb,

8 nM

[83]

39

DPV

ZnO and ZnO-poly glycine-modified carbon paste electrode

41

Other

DPV

Au-Pt-Pd-TiO2 nanotube-modified electrode

DPV

Carbon aerogel-molecular imprinted poly

M AN U

pyrrole 42

SWV

4.5 × 10-4 M

[84]

3 × 10-8 M

[85]

0.0004 µM

[86]

0.07 µM

[87]

0.08 µM

[88]

SC

40

RI PT

& Ni)

AuE-mercapto-terminated hexanuclear Fe (III) cluster

43

DPV

AuE-mercapto-terminated binuclear Cu (II) complex

EIS

PGE - boronic acid functional polythiophene

0.3 µM

[89]

45

DPV

Porous boron-doped diamond electrode

0.06 µM

[90]

46

DPV

GCE - N,N-bis(indole-3-carboxaldimine)-1,2-

0.186 µM

[91]

0.5 nM

[92]

-8

3.34 × 10 M

[93]

0.26 µmol L-1

[94]

TE D

44

diaminocyclohexane

48

ECL

FTO - poly(luminol–benzidine sulfate) electrode

EP

47

DPV

GCE - β-cyclodextrin-poly(N-

49

DPV

AC C

isopropylacrylamide)

CPE - poly(allylamine hydrochloride) (AuNPPAH)

50

Amperometry

Pt E - gold nanoparticles - PEDOT

0.2 µM

[95]

51

DPV

2D hexagonal boron nitride (2D-hBN) SP

0.65 µM

[96]

graphitic electrodes

52

ACCEPTED MANUSCRIPT

B] Serotonin Graphene

DPV

11.7 nmol L-1

GCE – RGO – polyaniline - MIP-Au NPs

53

DPV

GCE - electrochemical RGO - porphyrin

54

SWV

GCE - graphene nanomaterials (GO, RGO)

55

Amperometry

ITO - GR Au Ag nano alloy

Amperometry

GCE - GO poly lactic acid - Pd NPs

57

DPV

58

-3

[97]

4.9 × 10 µM

[98]

3.2 × 10-8 M

[44]

1.6 nM

[99]

-8

8 × 10 M

[100]

GCE – PEDOT - RGO - Ag nanocomposite

0.1 nM

[45]

DPV

GCE – RGO - cobalt oxide nanocomposite

48.7 nM

[101]

DPV

GCE – NiO – CNT - PEDOT

0.063 µM

[11]

60

DPV

CILE - Carbon IL - CoOH2 NPs - MWCNT

0.023 µM

[102]

61

DPV

GCE - metal oxides-MWCNT

118 nM

[51]

62

DPV

SPCE – MWCNT – ZnO -chitosan

0.01 µM

[103]

63

DPV

GCE – FCNT –IL - TiO2 NPs

28 nM

M AN U

CNT

TE D

59

SC

56

RI PT

52

[69] -1

DPV

Pt E - CNT - polypyrrole Ag NPs

0.15 µmol L

[50]

65

DPV

GCE – CNT - ILs

2 µM

[104]

66

DPV

GCE - Nafion - Ni(OH)2 – MWCNT composite

0.003 µmol L-1

[105]

67

DPV

GCE - carbon nanofibers

250 nM

[106]

68

CV

GCE – CNT - poly crystalline BDE

10 nM

[107]

69

Amperometry

0.2 nmol L-1

[108]

DPV

71

Metal&

DPV

72

Metal

DPV

AC C

70

EP

64

Glass – poly dimethyl siloxane - SWCNT

-8

GCE – FMWCNT - Chit

5 × 10 M

[49]

GSPE - polypyrrole Au NPs

33.22 nM

[108]

GCE - tungsten trioxide nanoparticles

1.42 nM

[109]

53

ACCEPTED MANUSCRIPT

73

oxides

74

SWV

GCE – Au NPs

2 × 10-8 M

[110]

DPV

GCE - Fe3O4 NPs – chit – poly(bromocresol

80 nM

[111]

76 77

DPV

Other

SPE - Cs-Au NPs

CV

FTO – PEDOT – PSS – TpyP – 3IP

DPV

2.5 × 10-10 M

[112]

0.23 µM

[113]

-8

GCE - calixarenes

-1

3 × 10 mol L

SC

75

RI PT

green)

-1

[114]

Amperometry

CPE - poly(2-amino-5-mercapto-thiadiazole)

0.4 nmol L

79

DPV

Poly pyrrole pencil graphite electrode

2.5 nM

[116]

80

DPV

Poly(melamine)-modified edge plane pyrolytic

30 nM

[117]

5 nM

[118]

M AN U

78

[115]

graphite sensor 81

DPV

Nafion membrane-coated colloidal gold SPE

MIP-Molecular imprinted polymer; CV-Cyclic voltammetry; DPV-Differential pulse voltammetry; SWV-Square wave voltammetry; EIS-Electrochemical impedance spectroscopy; NP-Nanoparticles; GO-Graphene oxide; ILs-Ionic liquids; PAN-Polyaniline; Chit-Chitosan; MWCNT-Multiwall carbon nanotubes; SWCNT-Single walled carbon

TE D

nanotubes; PEDOT- Poly(3,4-ethylenedioxythiophene); FTO-Fluorine-doped tin oxide, CILE-Carbon ionic liquid electrode, GCE-Glassy carbon electrode; SPCE-Screen printed

AC C

EP

carbon electrode, AuE-Gold electrode; PtE-Platinum electrode; ITO-Indium tin oxide; CPE-Carbon paste electrode; PGE-Pencil graphite electrode.

54

ACCEPTED MANUSCRIPT

Table 3 MOFs, MIPs, and metal- and metal oxide–based electrochemical sensors for detecting neurochemicals Sensor

Detection method

Neurochemicals Samples

1 2

G-ZIF8 Fe-MIL-88–H2O2-OPD

CV FS

DA DA

3

POMOF/RGO

CV

DA

4 5

RGO/ZIF-8 Zr-Porphyrin-MOF/MPC

DPV DPV

6 7

Nafion/C/Al-MIL-53-(OH)2 ZIF-8

DPV DPV

DA UA XA HX DA DA

A] MOFs

11

MIL-101

CV

12

GNe-Cu-MOF

Amperometry

13

UiO-66-NO2@XC-72

DVP

SC

M AN U Serum –a

TE D

ECL DPV DPV

Cow serum Hydrochloride injection and human urine –a

Urine and serum –a

DA DA AA DA UA DA UA H2O2 AA

–a –a

AA

Hydrochloride injection

Urine

EP

Fe-MIL-88 MOF Abtz–CdI2–MOF Mn-MOF/MWCNT

AC C

8 9 10

Linear range (µM)

LOD (µM)

Ref.

3-1000 0.05–30

1.0 0.046

[123] [20]

1.0– 200

0.0804

[133]

0.1–100 5–160 5–200 5–220 0.03–10 0.05–0.5

0.03 0.14 0.052 0.49 0.008 0.195

[124] [19]

1.0–20.0 1x10-6–1x10-2 0.25–50 0.1-1150 0.01-500 0.02-1100 5–250 30–200 10–11,180 0.5–6965.5

0.529 2.9 x10-7 0.057 0.01 0.002 0.005 –c

[130]

2 0.02

[134]

0.2–3.5

0.12

[131]

RI PT

N

–a –a

55

[125] [126] [127] [128] [129]

ACCEPTED MANUSCRIPT

DA UA DA AA DA DA

DVP SWV

16 17

luminol–H2O2–HKUST-1

CL

ZnO@ZIF-8

PL and ELC

18

Cu-hemin MOF/CS-RGO

CV

H2O2 AA H2O2

19 20 21

MIPs(NA)@CuO Poly(Py-PBA) MIS

CV DPV AD

DA DA DA

22 23

DPV DPV

24 25

3-D MIP arrays Imprinted silica matrix-poly (aniline boronic acid) PTA/AuNP–MIP GF/CNT/MIP

DPV CV

26

MIP/NPAMR

CV

27

MIP/hNiNS

CV

28 29

MIP-PANI PPy-MIP and OPD-MIP

CV, EIS and DPV DPV

Serum and urine –a

Plasma and urine Serous buffer solution –a

–

b

0.005 0.03 0.00067 –c –c 0.0023 –

c

[135] [132] [136] [137]

0.019

[138]

Serum Injection –a

0.02–25 0.05–10 0.1–1.0

0.008 0.033 0.014

[140] [141] [142]

EP DA

Hydrochloride injections Hydrochloride injection

1–10 and 10–800 0.05–500

–c 0.018

[15] [143]

DA DA

and human serum Human serum –a

0.001–5.0 2x10-9– 10-6

3.3x10-5 6.67x10-6

[21] [148]

EP

TE D

M AN U

0.065–410

B] MIPs

AC C

0.03–2 0.75–22 0.002–10 0–0.09 0–0.03 0.010–0.70

RI PT

Fe3O4@ZIF-8/RGO PMo10V2@MIL-101 (Cr)

SC

14 15

solution and urine

2x10-7– 2x10-2

6.83x10-8

[145]

DA

Rabbit serum and rat brain tissue Serum

5x10-8–5x10-5

1.7x10-8

[149]

AA DA

Serum –a

–b –b

1.0 7.9/3.9

[146] [14]

DA

56

ACCEPTED MANUSCRIPT

35

GO/SiO2-MIP

DPV

DA

5-HT DA NE EPI DA DA AA UA NE DA 5-HT Trp DA

SWV DPV CV

39 40

Au-RME PdNP/CM

CV CV

47 48

l-Cys/AuNPs/MWCNT NiO/CNT/PEDOT

DPV DVP

49

Nafion-SWCNT -[Co(bdmpzm)2(NCS)2]

SWV

0.05– 160

0.003

[155]

Human serum Human serum –a

0.1–15

[144] [158] [159]

–a

0.2–100.0 3.27–40.51 3.27–13.89

0.033 0.6 5.5/6.9 4.5/6.3 5.6/7.7 0.05 0.53 0.66 0.03 0.026 0.063 0.210 0.095

Hydrochloride injections and urine Urine

EP

AuNP@PPyNP PPyNW/PtNP Au/SAM/AuNP Au/SAM/AuNR

AC C

36 37 38

[147] [150] [151] [152] [153] [154] [22]

Tablets –a –a –a Urine and plasma

TE D

C] Metals and metal oxides

0.050–100 1–1000 0.625–100 0.5–40 0.048–50 1.0–100 0.02–800

Injection

RI PT

CV SEM and SWV DPV DPV DPV DPV DPV

SC

MIP/PPyNW MIP MIP/MWCNT MIP AuNPs@SiO2–MIP Carbon fiber/MIP ZNT-supported MIP

3.05/12 7.08/5.5 0.033 0.26 0.06 0.13 0.02 0.39 –c

M AN U

30 31 32 33 34 35 36

NE EP DA AA DA DA DA DA DA

Human serum Human serum Human serum

Urine

57

1–77 –b

0.2–100.0 0.03–20 0.3–35 1–41 –b

[160] [161] [162] [11]

[163]

ACCEPTED MANUSCRIPT

–a

CV DPV DPV PL

DP AA DA DA DA DA

Nano-MnOOH Tyrosinase/NiO/ITO

SWV CV

DA DA

–a

Cu/MnO2/MWCNT TiO2 AuNP-GO/Au-IDA

CV PEC CV

CA DA AA UA

51 52 53 54

CuNP AuNP@MIES AuNP-DNS/MWCNT BSA-Au NC

55 56 57 58 59

No application

b

No linear range

c

No limit of detection

0.044 7.5 5x10-5 0.0078 0.05 0.006

Fetal bovine serum –a

Mouse brain Urine

[164] [166] [167] [168] [169]

1.2–200 2–100

0.1 1.04

[170] [171]

0.6 –2 0.001–25 4.6–193 2–1050

0.34 0.15 10-3 1.4 0.62

[172] [23] [165]

TE D

a

–a –a –a Cerebrospinal fluid

0.2– 1 2 –200 10-4–1.0 0.02–0.54 0.8–400 0–0.01

RI PT

DVP

SC

BDD/MEA

M AN U

50

EP

AA: ascorbic acid; Abtz: 1-(4-aminobenzyl)-1,2,4-triazole); AD: amperometric detection; AuNP: gold nanoparticle; AuNR: gold nanorod; Au-

AC C

RME: Au-ring microelectrode; BDD-MEA: boron-doped diamond microelectrode array; CA: catecholamines; CL: chemiluminescence; CM: carbon monolith; CS: chitosan; CV: cyclic voltammetry; DA: dopamine; DPV: differential pulse voltammetry; ECL: electrochemiluminescence; EIS: electrochemical impedance spectroscopy; EPI: epinephrine; FS: fluorescence spectrophotometer; G: graphene; GF: graphene foam; GO: graphene oxide; Hb: hemoglobin; H2O2: hydrogen peroxide; HX: hypoxanthine; 5-HT: serotonin; IDA: interdigitated microelectrodes array; ITO: indium tin oxide; l-Cys: l-cysteine; MIPs: molecularly imprinted polymers; MIS: molecularly imprinted silica; MOF: metal–organic framework; MPC: macroporous carbon; MWCNT: multiwall carbon nanotube; NC: nanocluster; NE: norepinephrine; NiO: nickel oxide; NPAMR: nanoporous 58

ACCEPTED MANUSCRIPT

Au–Ag

alloy

microrod;

OPD:

o-phenylenediamine;

PEC:

photoelectrochemical;

PEDOT:

poly(3,4-ethylenedioxythiophene);

PO:

polyoxometalate; PL: photoluminescence spectroscopy; PPy: polypyrrole; PPyNP: polypyrrole nanoparticle; PPyNW: polypyrrole nanowire;

RI PT

PtNP: platinum nanoparticle; PTA: p-thioaniline; RGO: reduced graphene oxide; SAM: self assembled monolayer; SEM: scanning electron microscope; SWV: square wave voltammetry; Trp: tryptophan; UA: uric acid; XA: xanthine; ZIF: zeolitic imidazolate framework; ZNT: ZnO

AC C

EP

TE D

M AN U

SC

nanotube

59

ACCEPTED MANUSCRIPT

(B)

M AN U

SC

RI PT

(A)

AC C

EP

TE D

(B)

Fig. 1. (A) Schematic illustration of the electrochemical sensors for the determination of DA; (B) Differential pulse voltammograms of different concentrations of DA at GO-IL-AuNPs/GCE (pH ¼ 5.5). Inset: linear calibration curve in the range 7 nM to 5 mM DA; (C) The SEM images of (a) GO, (b) GO-IL, (c) AuNPs, and (d) GO-ILAuNPs. [42] 60

AC C

EP

TE D

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT

Fig. 2. (I) SEM images of MWCNT-chitosan nanocomposite film; (II) A) DPVs of serotonin of different concentrations (0.05– 16 mM) in PBS recorded at MWCNT-Chit/GCE. B) Plot of thepeak current against the concentration of serotonin [49].

61

A)

C)

TE D

M AN U

B)

SC

RI PT

ACCEPTED MANUSCRIPT

D)

EP

Fig. 3. A) Schematic diagram of the preparation procedure of the RGO/ZIF-8 nanocomposite and RGO/ZIF-8/GCE; B) X-ray diffraction patterns of GO, RGO, ZIF-8 and RGO/ZIF-8; C) SEM images of GO (a, b), RGO (c, d), ZIF-8 (e, f) and RGO/ZIF-8 (g, h) with different magnified times;

AC C

D) DPV curves of 1.0 ×10−4 M DA (curve a), 1.0 ×10−3 M AA (curve b), mixture of 1.0 × 10−4 M DA and 1.0 ×10−3 M AA based on RGO/ZIF8/GCE (curve c) and bare GCE (curve d) in 0.1 M PBS solution (pH 7.0) [124].

62

AC C

EP

TE D

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT

Fig. 4. Schematic showing sensor fabrication using ultrathin molecular imprinted polyaniline/graphite electrode and electrochemical sensing of ascorbic acid (AA) in bovine serum [146].

63

ACCEPTED MANUSCRIPT

M AN U

SC

RI PT

A)

AC C

EP

TE D

B)

64

ACCEPTED MANUSCRIPT

AC C

EP

TE D

M AN U

SC

RI PT

C)

Fig. 5. A) Scheme illustrates the mechanism for the formation of the NiO/CNT/PEDOT composite on the GCE; B) SEM images of (a) PEDOT, (b)

NiO/PEDOT,

(c)

CNT/PEDOT,

and

(d)

NiO/CNT/PEDOT

composites.

(e)

DPV

curves

of

bare

GCE,

PEDOT/GCE,

NiO/PEDOT/GCE,CNT/PEDOT/GCE, and NiO/CNT/PEDOT/GCE in pH 7.0 PBS containing 15 µM DA, 25 µM 5-HT, and 100 µM Trp; C) TEM images of (a) the CNTs and (b) the NiO/CNT/PEDOT composite. (c) Raman spectra of the CNTs and the NiO/CNT/PEDOT composite. (d) FTIR spectra of EDOT andthe NiO/CNT/PEDOT composite [11]. 65

Curriculum Vitae

ACCEPTED MANUSCRIPT

Distinguished Professor Ki-Hyun Kim Department of Civil & Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul 04763, Korea

RI PT

Email: [email protected] (or [email protected]) ☏ 82-2-2220-2325 Fax -1945

•

Brief Summary (8 June 2018) • Google Total Citation (~13,829), Google H-Index=56 • •

Research Gate

697

PUBLICATIONS

SC

•

RG Score 50.47 Reads 106k

M AN U

1] Main home -> http://environment.cafe24.com/ 2] Research Gate -> https://www.researchgate.net/profile/Ki_Hyun_Kim4 3] Google Scholar -> http://scholargoogle.com/citations?user=RpkzepcAAAAJ&hl=en&oi=ao

[A] Biography

Prof. Ki-Hyun Kim was at Florida State University for an M.S. (1984-1986) and at University of South Florida for a Ph.D. (1988-1992). He was a Research Associate at ORNL, USA (1992 to 1994). He moved

TE D

to Sang Ji University, Korea in 1995. In 1999, he joined Sejong University. In 2014, he moved to the Department of Civil and Environmental Engineering at Hanyang University. His research areas broadly cover the various aspects in the field of “Air Quality & Material Engineering” in connection with advanced novel materials like Coordination Polymers. He was awarded as one of the top 10 National Star Faculties in

EP

Korea in 2006. He is a serving editorial board member of several journals (e.g., Environmental Research, Atmospheric Pollution Research, and Sensors). He has published more than 530 articles, many of which

AC C

are in leading scientific journals like ‘Chemical Society Reviews’, ‘Progress in Material Science’, ‘Progress in Polymer Science’, ‘Coordination Chemistry Reviews’, and ‘Trends in Analytical Chemistry’. [B] Research Areas

Prof. Ki-Hyun Kim has been working on the following R & D areas: -Development and establishment of detection methods for environmental pollutants (VOCs and heavy metals) along with the establishment of basic QA for those pollutants. -Development and performance evaluation of diverse sorbent materials for thermal desorption of VOCs. -Sorptive removal and regeneration cycle in the treatment of environmental pollutants with MOFs. 1

ACCEPTED MANUSCRIPT

[C] Personal Birthdate: 27 October 1961

Birthplace: Dae-Gu, Repulic of Korea (South) Marital Status: Married, one child

Job History

RI PT

March 2014 - Professor, Hanyang University 2008 – Feb. 2014 Professor, Sejong University 2002 – 2007 Associate Professor, Sejong University 1999-2002 Assistant Professor, Sejong University

SC

1995-1998 Lecturer & Assistant Professor, Sang Ji University 1992-1994 Research Associate, Oak Ridge National Lab.

1992-1994 Research and Teaching Assistant, University of South Florida

M AN U

1984-1986 Research Assistant, Florida State University

Education

1992 Ph.D. Marine & Atmospheric Science , University of South Florida 1986 M.S. Marine & Atmospheric Science, Florida State University

Honors

TE D

1984 B. S. Mineral & Petroleum Eng., Han Yang University

May 2018 Baik Nam Distinguished Professor

EP

May 2018 NRF Scientist of Korea

March 2017 Top Researcher in HYU Award

AC C

2001-2011 Prominence Scientist - Sejong University Nov. 2006 National Star Faculty of Korea Award - Korean Research Foundation 2003 Best Accomplishment Award - Korean Science & Engineering Foundation 2003 Best Article Award - Korean Ministry of Science & Technology 2002 Best Article Award - Korean Society of Atmospheric Environment 2001 Best Scholarly Award - Korean Earth Science Society 1981-1984 Han Yang University Overseas Study Fellowship Award

2

[D] List of Top 10 publications in recent years (http://environment.cafe24.com/articles.php)

ACCEPTED MANUSCRIPT

Prof Kim published more than 540 peer-review SCI journal articles with more than 85% as the corresponding (or first)

AC C

EP

TE D

M AN U

SC

RI PT

[1] Kumar P., Deep A., Kim K.-H.*, Brown R.J.C. (2015) Coordination polymers: Opportunities and challenges for monitoring volatile organic compounds. Progress in Polymer Science 45, 102-118. (IF=25.766) [2] Mehta J., Bhardwaj N., Bhardwaj S.K., Kim K.-H.*, Deep A.* (2016) Recent advances in enzyme immobilization techniques: metal-organic frameworks as novel substrates. Coordination Chemistry Reviews 322, 30-40 (IF 13.324) [3] Kumar V., Kim K.-H.*, Kumar P., Jeon B.-H., Kim J.-C. (2017) Functional hybrid nanostructure materials: Advanced strategies for sensing applications toward volatile organic compounds. Coordination Chemistry Reviews 342, 80-105. (IF 13.324) [4] Kumar P., Kim K.-H.*, Bansal V., Kumar P. (2017) Nanostructured materials: A progressive assessment and future direction for energy device applications. Coordination Chemistry Reviews 353, 113-141. (IF 13.324) [5] Vellingiri K., Philip L, Kim K.-H.* (2017) Metal-organic frameworks as media for the catalytic degradation of chemical warfare agents. Coordination Chemistry Reviews 353, 159-179. (IF 13.324). [6] Kumar P., Pournara A., Kim K.-H.* Bansal V., Rapti S., Manos M.J.* (2017) Metal-organic frameworks: Challenges and opportunities for ion-exchange/sorption applications. Progress in Materials Science 86, 25-74. (IF 31.14) [7] Kumar S.*, Rani R, Dilbaghi N, Kumar T, Kim K.-H.* (2017) Carbon nanotubes: A novel material for multifaceted applications in human healthcare. Chemical Society Reviews 46, 158-196. (IF 38.618) [8] Vellingiri K., Kim K.-H., Pournara A., Deep A. (2018) Towards high-efficiency sorptive capture of radionuclides in solution and gas. Progress in Materials Science 94, 1-67. (IF=31.14) [9] Kumar S., Alhan S., Nehra M., Dilbaghi N., Tankeshwar K., Kim K.-H. (2018) Recent advances and remaining challenges for polymeric nanocomposites and their health care applications. Progress in Polymer Science 80, 1-38. JR (IF=25.766) [10] Kumar S.*, Nehra M., Kedia D., Dilbaghi N., Tankeshwar K., Kim K.-H.* (2018) Carbon nanotubes: A potential material for energy conversion and storage. Progress in Energy and Combustion Science 64, 219-253. (IF 17.382)

3