Electrochemical sensor based on SmHCF/multiwalled carbon nanotube modified glassy carbon electrode for dopamine

taher yousefi ¹ ( )
Ghasem Adollahi ² ( Kharazmi university )
Mohammad hossein mashadizadeh ³ ( Kharazmi University )
ramin yavari ⁴ ( NSTRI )

تاريخ الإرسال : 11 الأحد , جمادى الثانية, 1442 تاريخ التأكيد : 24 الثلاثاء , ذو الحجة, 1442

الکلمات المفتاحية: sensor, Dopamine, Modified electrode, Electrochemical, SmHCF/(MWCNT),

ملخص المقالة :

SmHCF/(MWCNT) nano structures modified glassy carbon (GC) electrode was used as electrochemical sensor for the electro oxidation of dopamine. Our strategy was the combination of high electrocatalytic property of SmHCF to electroactive biomolecule and high conductivity, surface area and adhesive properties of carbon nanotubes. The presence of SmHCF nanoparticles and MWCNT were approved by Scanning electron microscopy (SEM) and cyclic voltammetry (CV). The electrocatalytic performance of GC, SmHCF-GC, MWCNT-GC and SmHCF-MWCNT-GC electrodes toward dopamine was compared and the results cleared the enhanced electrocatalytic activity of SmHCF-MWCNT-GC (lowering the potential of the oxidation process and increased oxidation current peak.) relative to others. This unique combination leads to improvement of the sensitivity of dopamine determination. The differential pulse voltammetry was used for quantitative determination of dopamine. The linear dynamic range relationship between oxidation peak currents and dopamine concentration was 2× 10-7 - 5× 10-6 (slope = 24.187 µAµM-1) with the detection limit of 6× 10-8 for DA. The sensitivity of the electrode was 24.187 µAµM-1 that it is very high relative to reported works. The relative standard deviation (RSD) of the reproducibility (5 modified electrodes), repeatability (successive 10 times), and stability (50 days) of the modified electrode were 3%, 3% and 2.5% respectively. The accuracy and selectivity of the modified electrode were indicated in the real sample as human serum samples and in the presence of possible interfering agents. Good selectivity and recovery were observed for modified electrode.

نص كامل:



 

Electrochemical sensor based on SmHCF/multiwalled carbon nanotube modified glassy carbon electrode for dopamine

Abstract

SmHCF/(MWCNT) nano structures modified glassy carbon (GC) electrode was used as electrochemical sensor for the electro oxidation of dopamine. Our strategy was the combination of high electrocatalytic property of SmHCF to electroactive biomolecule and high conductivity, surface area and adhesive properties of carbon nanotubes. The presence of SmHCF nanoparticles and MWCNT were approved by Scanning electron microscopy (SEM) and cyclic voltammetry (CV). The electrocatalytic performance of GC, SmHCF-GC, MWCNT-GC and SmHCF-MWCNT-GC electrodes toward dopamine was compared and the results cleared the enhanced electrocatalytic activity of SmHCF-MWCNT-GC (lowering the potential of the oxidation process and increased oxidation current peak.) relative to others. This unique combination leads to improvement of the sensitivity of dopamine determination. The differential pulse voltammetry was used for quantitative determination of dopamine. The linear dynamic range relationship between oxidation peak currents and dopamine concentration was 2× 10-7 - 5× 10-6 (slope = 24.187 µAµM-1) with the detection limit of 6× 10-8 for DA. The sensitivity of the electrode was 24.187 µAµM-1 that it is very high relative to reported works. The relative standard deviation (RSD) of the reproducibility (5 modified electrodes), repeatability (successive 10 times), and stability (50 days) of the modified electrode were 3%, 3% and 2.5% respectively. The accuracy and selectivity of the modified electrode were indicated in the real sample as human serum samples and in the presence of possible interfering agents. Good selectivity and recovery were observed for modified electrode.

Keyword: Dopamine; SmHCF/(MWCNT); Modified Electrode; Electrochemical; Sensor

 

1.       Introduction

One of the important neurotransmitter from catecholamine family in mammalian central nervous is Dopamine (DA), 4-(2-aminoethyl) benzene-1,2-diol. This neurotransmitter has serious function in the control of central nervous, renal, cardiovascular, and hormonal systems. In addition to Parkinson, Alzheimer and Schizophrenia and Schizophrenia disease the dopamine also involved in the drug addiction (Behzad et al. 2015; Mashhadizadeh et al. 2012). DA acts as a local chemical messenger, like a vasodilator, to reducution of insulin production or regulation of lymphocytes activity (Stela et al. 2015). Hence the exact determination of dopamine concentration in biological fluids is very important. Several techniqes such as colorimetry (Yumin et al. 2015), LC–MS/MS (Daping  et al. 2016), HPLC-MASS spectroscopy (Na et al. 2016; Yongrui et al. 2016; Gottas et al. 2015),  HPLC- fluorescence (Maofang et al.2016; Giuseppe et al. 2014),  fluorescence, electrophoresis (Hai et al. 2013; Yu et al. 2014; Yunsha et al. 2011) and electrochemical methods (Behzad et al. 2015; Mashhadizadeh et al. 2012; Lin et al. 2016; Qiu  et al. 2015; Can  et al. 2015) have been reported for DA determination in various samples.

Among mentioned methods electrochemical techniques have advantages such as, low detection limit, low sample and solvent consumption, low matrix effects upper sensitivity, simplicity, affordability, suitability for real-time detection, reproducibility and high-speed analysis. In electrochemical methods for improvement of analytical merits such as sensitivity, selectivity and detection limit the surface of electrodes are physically and chemically modified with suitable modifiers (Behzad et al. 2015; Adel et al. 2020; Zorione et al. 2014).

One of the most favorite modifier groups is metal hexacyanoferrates (MHCFs). These materials as mixed-valence compounds have nice properties and play important role in various areas such as electroanalysis etc.(Deng et al. 2015; Venkatesan et al. 2021; Vinu et al. 2014; Gholivand et al. 2013; Sattarahmady et al. 2013; Heli et al.2012; Mashadizadeh et al. 2016)

 Electrochromism (Liao et al. 2016; Kao et al. 2014; Hong and Chen 2010) production (Padigi et al. 2015; Jia et al.2015; Jayalakshmi and Scholz 2000) ion exchange (Karnjanakom et al. 2014) ion selectivity (Chen et al. 2013) They are also used in biosensors and solid state batteries (Baldo et al. 2014; Rajkumar et al. 2013; Fang et al. 2011; Noroozifar et al. 2010).

The low adhesion property of ultrafine nanoparticles limit the using of metal hexacyanoferrates as modifier on electrode surface, as MHCF particles splash into solution during the analysis process. In sensor using metal hexacyanoferrates materials to prevent the mentioned problem, usually the metal hexacyanoferrates particles are mixed/ or dispersed in suitable wrapper conductive materials. For example composites containing MHCFs such as MHCF-conducting polymers (1) MHCF-graphene oxide/carbon nanotubes (19) MHCF-carbon nanotubes (Rajkumar et al. 2013), MHCF graphene (Sattarahmady et al. 2013), have been reported for tackle the mentioned problem. Carbon Nanotube (CNT) is one of the important allotrope of carbon (others are the fullerene, diamond and graphene) with a cylindrical structure in nanoscale diameter. The CNTs have attracted much attention since their discovery in 1991 (Manasa et al. 2018). The high electrical conductivity, high electrocatalytic effect, excellent biocompatibility and strong adsorptive ability are the unique properties of the CNTs (Ren et al. 2011; Zhang et al. 2015; Tootoonchi et al. 2018; Sheetal et al. 2017). Multiwalled Carbon nanotubes (MWCNTs), possess the unique structure and properties (including large surface areas, stability and rich surface chemical functionalities)  (43). The solar cells, batteries (Ren et al. 2011), actuators (Zhang et al. 2015; Svorc et al. 2013; Habibi et al. 2014; Li et al. 2013; Pournaghi-Azar and Saadatirad 2010; Ensafi et al. 2015; Mashhadizadeh and Rasuli 2014) and glucose sensing (Tootoonchi et al. 2018) are important industrial applications of MWCNTs. Besides the good folder property, of the MWNTs, they act as new electron meditator and promote electron transfer process, especially in the electrochemical reactions (Mazloum-Ardakan et al. 2011).

In the current work a simple, facile and rapid route to modification of glassy carbon electrode with MWCNTs and Samarium Hexacyanoferrate (SmHCF) for the determination of DA will be introduced. The good adhesive property of MWCNT (for the improvement of the sensor stability and durability) and good catalytic effect of SmHCF nanoparticles for catalytic oxidation of dopamine were our strategy in this work. The electrode modified in two simple steps process including the drop casting of MWCNTs on GCE electrode followed by electrodeposition of SmHCF. The prepared electrode was characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS) and cyclic voltammetry (CV). The MWCNTs/SmHCF modified electrode successfully electrocatalyze the DA and is quantified in real system serum sample using differential pulse voltammetric (DPV) method. It was found that the modified electrode not only exhibited strong electrocatalytic activity for oxidation of DA but also showed great stability and durability.

2. Experimental

2.1. Chemicals

Dopamine hydrochloride (DA) was purchased from Tehran drug Pharmaceutical Company (Tehran, Iran). All reagents were of analytical grade and were used as received. The DA stock solutions of 1 × 10-2 mol L-1 were prepared by dissolving the appropriate amount of this drug in distilled water in 25 mL volumetric flask. To minimize decomposition, the stock solution was stored in the dark and under refrigeration. Standard solutions of this drug with lower concentrations were prepared daily by diluting the stock solution with distilled water. All solutions were prepared with double distilled water. The supporting electrolyte was phosphate buffer solution (PBS, 0.1 mol L-1, pH 7). Samarium nitrate Hexahydrate  (99%)was obtained from Aldrich and used without further purification. Sodium chloride (99%) and potassium hexacyanoferatte (99%) were obtained from Merck. The MWNTs were bought from Iran's Research Institute of Petroleum Industry and synthesized by chemical vapor deposition (CVD) with a diameter of 8–15 nm, a length of 50 μm and the purity of 95%.

2.2. Apparatus

All voltammetric measurements were carried out with a Palm Sens (EmStat instrument 3, The Netherlands) controlled by software PSTrace. A standard three-electrode cell was used for all electrochemical experiments. The bare glassy carbon electrode (GCE) and MWCNTs/SmHCF modified electrode were used as working electrodes. A platinum wire served as a counter electrode and all the potentials were relative to an Ag/AgCl/KCl (3.5 mol L-1) reference electrode. The pHs of the solutions were controlled by a Metrohm pH/mV meter M-827 (Switzerland).

2.3 Preparation of MWCNTs and electrochemical fabrication of MWCNTs/SmHCF  composite modified electrode

The GC electrode was polished carefully with 0.05µm alumina slurry on a polishing cloth, and then washed ultrasonically in ethanol and water, respectively. 0.1mg of the untreated MWNTs was added to 5mL of nitric acid (wt. 65%), the mixture was sonicated for about 3 h to obtain a relatively stable suspension. The cleaned GCE was coated by casting 20µL of the black suspension of MWNTs in nitric acid and dried in an oven at 50 ◦C to remove the acid. Then the MWNTs modified GCE was washed with water until the remained acid was completely separated (Rezaei et al. 2008). The solution for preparation of the SmHCF, using the electrodeposition method, was a 5 mM Sm(NO3)3 + 5mM K3Fe(CN)6 solution containing 0.2 M NaCl and freshly prepared each time just before the experiments. The SmHCF was deposited on the surface of the MWNTs /GC electrode by potential cycling from +0.8 to -0.2 V at a sweep rate of 50 mV/s for 20 cycles (about 13 min) in the above solutions. The SmHCF was found to grow on the surface of the MWNTs/GC electrode with each potential cycle, as revealed by the change of peak currents with each cycle (Wu et al. 2004). Finally, the electrode was rinsed thoroughly with distilled water (Wu et al. 2004).

2.4 Preparation of Human Serum Sample

Determination of DA was carried out in human serum sample. The prepared modified electrode was applied to the analysis of the human serum samples using the standard addition method. The serum sample was initially centrifuged. After filtering, the sample was diluted 10 times with 0.1 M phosphate buffer of pH 7.0 (Shahrokhian et al. 2009). The diluted serum sample was spiked with different amounts of standard DA. Finally, after 30 min its DPV was recorded using the modified electrode.

3 Results and Discussion

3.1. Electrodeposition of SmHCF on the surface of the MWCNTs/GC electrode

A solution of 5 mM Sm(NO3)3, 5 mM K3Fe(CN)6 and 0.2 M NaCl (as supporting electrolyte) was used for synthesis of SmHCF nanoparticles. The SmHCF nanoparticles were deposit on MWCNTs/GC electrode surface by cyclic voltammetry technique (Fig. 1). It is clear that the redox peak currents of the Fe(CN) 63-/4- couple is decreased gradually with increase of the scan cycles, which confirms the formation of SmHCF on the electrode. In other word the potential of SmHCF formation overlapped with the potential of Fe(CN)63-/ Fe(CN)64 reaction. The Sm3+ ‏ion reacted instantaneously with Fe(CN)64- to form and deposit of SmHCF on the electrode surface. The mechanism of SmHCF formation on electrode surface is as the following EC reaction mechanism.

 

Fe(CN)63-  + e-          Fe(CN)64-       (electrochemical reaction ) (1)

Fe(CN)64-  + Sm3+  + Na+                        NaSmFe(CN)6       (chemical reaction)        (2)

 

 

 

Fig 1. Voltammograms of the SmHCF electrodeposition on the surface of the MWCNTs/GC electrode in a solution of 5 mM Sm(NO3)3 , 5 mM K3Fe(CN)6, and 0.2 M NaCl.

3.2 SEM

Fig. 2 (a,b) shows SEM images of the MWCNTs/GC and SmHCF/MWCNTs/GC modified electrode. Fig. 2a shows image of MWCNT modified electrode, as can be seen the surface of glassy carbon electrode has been uniformly covered by nanotubes uniformly (by well dispersed in nitric acid no entwined of nanotubes was take place). Fig. 2b shows the surface morphology of the SmHCF-MWCNTs modified electrode. To approve the presence of SmHCF nanoparticles on the electrode surface, the EDS was performed on electrode surface. Fig.  2 (inset) shows the EDS spectra of modified electrode, in the spectrum the peaks of Sm, Fe elements are shown clearly.

 

Fig. 2 SEM images of GC electrode modified with (a) MWCNTs and (b) SmHCF/MWCNTs; EDS spectra (inset)

 

 

 

 

 

 

3.3 Catalytic oxidation of Dopamine at the SmHCF/MWCNTs/GC modified electrode

 A bare GC, SmHCF-GC, MWCNTs -GC and SmHCF-MWCNTs-GC electrodes were used for study of electrochemical behavior of DA in 0.1 M phosphate buffer solution ( pH 7.0) contain of 1× 10 -5 M of DA (Fig. 3). As can be seen it is clear that the bare GC, MWCNTs -GC and SmHCF-GC electrodes do not show a indicated redox peaks for DA. While a sharp redox peak of DA at +0.22 V on SmHCF/ MWCNTs electrode, can be seen clearly which confirm the electrocatalytic property of SmHCF/ MWCNTs electrode toward DA species. The instability of SmHCF modified electrode and splashing of SmHCF particles into solution during work is the absolute reason behind of absence of redox peaks of DA on SmHCF- electrode. The improved and boosted redox peaks of DA at +0.22 V on SmHCF/ MWCNTs modified electrode are due to the synergistic effect of SmHCF and MWCNTs. The voltammograms of SmHCF/ MWCNTs electrode in the absence and presence of DA (1× 10 -5 M) are recorded in 0.1 M phosphate buffer solution with pH 7.0 as supporting electrolyte (Fig. 4). In the absence of DA or a blank solution (curve a), the redox peak was not observed in the potential range of -0.3 to 1.0 V which clarified that the SmHCF and MWCNTs were non-electroactive in this potential window. When 1× 10 -5 M of DA was dropped to blank solution (curve b) a sensitive and an apparent anodic peak in 0.22 V was observed which confirms the electrocatalitic oxidation of DA by SmHCF- MWCNTs-GC electrode.

 

Fig. 3 Cyclic voltammograms of (a) bare, (b) SmHCF modified, (c) MWCNTs modified, and (d) SmHCF- MWCNTs modified GC electrode sin 0.1 M phosphate buffer solution (pH 7.0) in the presence of 1× 10 -5 M of

DA

 

Fig. 4 Cyclic voltammograms of SmHCF- MWCNTs modified GC electrode sin 0.1 M phosphate buffer solution (pH 7.0) in (a) absence and (b ) presence of DA (1× 10 -5 M).

 

3.4 Scan Rate

 

For study of the reaction kinetics, the DA redox peak on the SmHCF-MWCNTs–GC at the different scan rates (ʋ: 20-500 mV/s) were recorded (Fig. 4a).

 

 Fig. 4(a) CVs at different scan rates for the SmHCF- MWCNTs modified GC electrode in 0.1 M PBS (pH 7.0). (b) Peak current vs. scan rate plot; (c) plot of log (peak current) vs. log (scan rate); plot of E(v) vs. log(v/mv/s).

The results indicated that an oxidation and a reduction peaks are present in all scan rates, confirming irreversibility of DA behavior on SmHCF-MWCNTs–GC electrode. Also the results show that anodic currents increased linearly by increasing the scan rate and potential positively shifted gradually). The relationship between peak current and log ʋ was linear, indicating the DA reaction on electrode is an adsorb-controlled irreversible process. The relationship (linear) between peak currents and scan rates is as following equation:

Ipa = 0.982 logʋ + 0.1579 (Ipa in µA, ʋ in mV s−1, R2 = 0.991)

3.5 pH Effect on Voltammetric Responses

It is well known that the pH of the supporting electrolyte has an important effect on the electrooxidation of DA at the electrode surface. Different pH values ranging from 5.8–8.5 in a 1 ×10-5 M solution of DA were selected for study of pH influence on voltammograms the potential scan rate was 100 mV s−1 (Fig.6). The results show that the peak potential has negative shift with increasing pH, which suggests that H+ participates in the oxidation process. The maximum anodic peak current was observed at pH 7.0 (Fig.6a). Therefore, pH 7.0 was chosen for further studies of DA. At the 5.8 - 8.5pH range a good linear relationship was observed between the Epa and the pH values (Fig 6b), the relationship can be expressed as following:

Epa (mV) =  0.6794 - 0.0628 pH R² = 0.9930

The slope of the linear curve of Epa vs. pH was approximately equal to - 0.0628 mV vs. pH unit which is close to the expected value of 0.059 mV vs.  pH. This shift indicates that equal numbers of electrons and protons are involved in the oxidation of DA on the SmHCF-MWCNTs–GC surface. According to the results, and reports the following mechanism was suggested for oxidation of DA. (Scheme 1) (1).

 

pH increase

 

 (Fig.6). CVs of 1×10−5 M DA recorded at 5.8–8.5 range and a scan rate of 100 mV s−1. (a) Plot of the anodic peak current versus the pH value, ( b ) plot of the anodic peak potential versus pH

 

Scheme 1. Electrooxidation mechanism of DA

 

 

 

 

 

3.6 Influence of Accumulation Time

The cyclic voltammetry was used for studying the influence of accumulation time on intensity of oxidation current peak. As can be seen from Fig. 7, the anodic current is increased with accumulation time up to 210 s and then is decreased. The decrease of the oxidation peak after 210 s indicates completely saturation of electrode surface at 210 s and DA desorption after then. So, the accumulation time of 210 s was considered as an optimum time for subsequent experiments.

 

Fig.7 Influence of accumulation time of the oxidation peak currents for DA at modified electrode

 

3.7 Differential pulse voltammetric determinations

The DPV technique by modified electrode was used to determination of DA in 0.1 M phosphate buffer solution (pH 7.0). The influence of electrochemical parameters such as, pulse amplitude, pulse width, and scan rate were studied. The best result (high sensitivity) was obtained under condition of: 50 mV, 50 ms, and 30 mVs -1 for pulse amplitude, pulse width, and scan rate, respectively. The DPVs at various concentrations of DA are shown in Fig. 8a. The linear relationships between oxidation peak currents (Ipa) and DA concentration was: 2× 10-7 - 5× 10-6 (slope = 24.187 µAµM-1), with a detection limit of 6× 10-8 for DA. The linear regression equation was:

 

Ipa (µA)= 24.187 CDA(µM) + 11.581 R2 = 0.9907

 

Fig.8 (a) Ads- Differential pulse voltammograms of SmHCF/MWCNTs/GC electrode in PBS (pH 7.0) for the successive additions of DA, (b) plot of peak current as a function of the concentration of DA. [Scan rate 30 mV s−1; pulse amplitude 50 mV; pulse width 50 ms].

 

 

 

 

Table 1. Comparison of the efficiencies of various electrodes in the determination of DA.

Working Electrode	Technique	Linear Range	Detection Limit	senstivity	Reference
NG/NiTsPc/GCE	DPV	0.1-200	0.1	0.926	(Xu et al. 2016)
RGO-Pd-NPs/GCE	LSV	1-150	0.233	0.00262	(Palanisamy et al. 2013)
GNS/PEI/AuNP/GCE	DPV	1-83	0.2	0.2	(Ponnusamy et al. 2014)
MWCNT-nano FeTSPc/GCE	SWV	0-60	0.098	0.314	(Fashedemi and Ozoemena 2011)
SDS micelles/CPE	DPV	8–134	3.70	0.106	(Colín-Orozco et al. 2012)
PG/GCE	CV	5-710	2.0	0.1125	(Qi et al. 2015)
SGN/NiPc	DPV	40-1080	0.26	0.104	(Barros et al. 2013)
NiHCF–PNH/Au	DPV	0.01-10	0.021	3.27	(Behzad et al. 2015
SmHCF/MWCNTs/GCE	DPV	0.2-5	0.06	24.187	This work

 

The sensitivity, linear concentration ranges and detection limits of modified electrode for the determination of DA were compared with reported sensors (Table 1). As can be seen the sensitivity of our modified electrode is very higher than other biosensors, the sensitivity was 24.187 µAµM-1. Sensitivity is a very important sensor factor. The linear concentration rang and detection limits is acceptable.

3.8 Reproducibility, Repeatability, and Stability of the SmHCF/MWCNTs/GC electrode

The stability, repeatability and reproducibility of the modified electrode were determined as following. For study of electrode stability the DPVs of 50 µM DA solution were recorded over 50 days (every 10 days). The relative standard deviation (RSD) of DA oxidation peak after 50 days was 2.5%, which suggested satisfactory long time stability of electrode. The repeatability of the response of the modified electrode, was determined in a solution of 50 µM DA repeatedly for successive 10 times and the calculated RSD was 3%, which showed logical repeatability of modified electrode. For study of inter-day reproducibility of the modified electrode 5 modified electrodes were prepared at different days with a same preparation methods. The RSD value for the peak current of 50 µM DA with these electrodes was obtained as 3%, which showed satisfactory reproducibility of modified electrode.

3.9 Interference studies     

 

The selectivity of modified electrode was studied in the presence of the possible interfering agents influencing the determination of DA in solution 50 µM DA. Usually the interfering is serious when it changes the target signal more than 5%. Table 2 shows the results of typically ions and biomolecules which present beside of DA in the real samples and have interference potential in DA determination. It is clear that the oxidation peak current of DA was not affected seriously by substantial addition of cations, anions and organic molecules. Two compounds that commonly found with DA and could more potentially interfere with the determination of DA are UA and AA. The influence of UA and AA were studied under the optimum conditions (Fig. 9).  Thus the results demonstrated the sufficient selectivity of modified electrode in the voltammetric determination of DA.

 

Fig.9 Differential pulse voltammograms of SmHCF/MWCNTs/GC electrode in PBS (pH 7.0) for the DA, in presence of AA and UA

Table 2. Effect of interferences on the determination of DA (50 µM ) on modified electrode..

Interfering agent	Concentration (mM)	Signal change (%)
Zn2+, Mg2+, K+, Na+,	5	<0.3
Cl−, NO3−, PO43−	5	<1.0
Glucose	3	+4.5
Urea, uric acid	10	+3.0
Ascorbic acid	5	+2.0

 

   3.10 Real sample analysis

For determined the sensor ability of modified electrode in the real samples, the determination of DA in human serum was studied. The content of DA in sample was estimated by applying

DPV method. The results are summarized in Table 3. As can see the electrode shows satisfactory ability in real samples.

 

Table 3 Determination of DA in the serum samples used the modified electrode.

serum	Added (µM)	Found (µM)	Recovery (%)
1	0.50	0.47 (±0.02 )	94.00
2	1.00	0.97 (±0.03 )	97.00
3	20.00	20.20 (±0.05 )	101.00
4	50.00	52.00 (±0.04 )	104.00
5	100.00	103.00 (±0.03 )	103.00

 

Conclusion

The highest synergistic activity for dopamine oxidation was observed with modification of glassy carbon (GC) using of Sm[Fe(CN)6] nanoparticles and multi wall carbon nanotube. The roles of Sm[Fe(CN)6] nanoparticles and MWCNT were considered as electrocatalyst and binder respectively. In the absence of SmHCF nanoparticles the electrocatayist property was not observed. Also the absence of MWCNT the stability of electrode was low and Sm[Fe(CN)6] splashed to solution. The modified electrode was characterized with Scanning electron microscopy (SEM) and cyclic voltammetry (CV). The modified electrode shows improved electrocatalytic activity for electrochemical oxidation of dopamine. The dopamine concentration was determined by differential pulse voltammetry. The linear dynamic range relationship between oxidation peak currents and dopamine concentration was 2× 10-7 - 5× 10-6 (slope = 24.187 µAµM-1) with the  detection limit of  6× 10-8 for DA. The outstanding analytical merits of current work was sensitivity of the modified electrode: 24.187 µAµM-1 that it is very high relative to reported works. The accuracy of the modified electrode was investigated in human serum as the real sample and the selectivity of modified electrode was studied in the presence of possible interfering agents and satisfactory results were observed.

 

 

 

 

References

Afkhami A, Khoshsafar H, Bagheri H, Madrakian T (2014) Facile simultaneous electrochemical determination of codeine and acetaminophen in pharmaceutical samples and biological fluids by graphene–CoFe2O4nancomposite modified carbon paste electrode. Sensors and Actuators B, 203: 909–918.

Adel A.A, Elseman A.M, Alotaibi N.F, Nassar A.M, (2020) Simultaneous voltammetric determination of ascorbic acid, dopamine, acetaminophen and tryptophan based on hybrid trimetallic nanoparticles-capped electropretreated grapheme, Microchemical Journal

156: 104927

Alizadeh T, Mirzagholipur S (2015) An outstandingly sensitive enzyme-free glucose sensor prepared by co-deposition of nano-sized cupric oxide and multi-walled carbon nanotubes on glassy carbon electrode. Biochem Eng J 97: 81-91.

Arbab AA, Sun KC, Sahito IA, Qadir MB, Jeong SH (2015) Fabrication of highly electro catalytic active layer of multi walled carbon nanotube/enzyme for Pt-free dye sensitized solar cells. Appl. Surf. Sci 349: 174-183.

Baldo TA, Seraphim PM, Gomes HM, Teixeira MFS (2014) Glucose Biosensor Based on the Hexacyanoferrate 11-Mercaptoundecyl-N’,N”,N”’-Trimethylammonium/6- (Ferrocenyl) Hexanethiol.  Procedia Eng 87: 300-303.

Barros SBA, Rahim A, Tanaka AA, Arenas LT, Landers R, Gushikem Y. (2013) In situ immobilization of nickel(II) phthalocyanine on mesoporous SiO2/C carbon ceramic matrices prepared by the sol–gel method: Use in the simultaneous voltammetric determination of ascorbic acid and dopamine. Electrochim Acta 87:140–147.

Behzad R, Malihe Khalili B, Ali A E (2015) Fabrication of DNA, o-Phenylenediamine And Gold Nanoparticle Bioimprinted Polymer Electrochemical Sensor for the Determination of Dopamine. Biosens Bioelectron 66: 490–496.

Can D, Rabih K, Elmar L, Jakob H J, Jochen Kieninger,Christoph E. Nebel, Jürgen Heinze, Gerald A. Urbana. (2015) Nanocrystalline boron-doped diamond nanoelectrode arrays for ultrasensitive dopamine detection. Electrochim Acta 185:101–106.

Chen R, Tanaka H, Kawamoto T, Asai M, Fukushima C, Na H, Kurihara M, Watanabe, M. Arisaka M, Nankawa T(2013) Selective removal of cesium ions from wastewater using copper hexacyanoferratenanofilms in an electrochemical system Electrochim Acta 87:119–125.

Colín-Orozco E, Ramírez-Silva MT, Corona-Avendaño S, Romero-Romo M, Palomar-Pardavé M (2012) Electrochemical quantification of dopamine in the presence of ascorbic acid and uric acid using a simple carbon paste electrode modified with SDS micelles at pH 7. Electrochim Acta 85:307–313.

Daping Z, Lei W, Diana S-L. C, Vincent HT, Danielle R R (2016)Quantitative determination of dopamine in human plasma by a highly sensitive LC–MS/MS assay: Application in preterm neonates. J Pharm Biomed Analy 117: 227–231

Deng K, Li C, Qiu X, Zhou J, Hou Z (2015) Synthesis of Cobalt hexacyanoferrate decorated graphene oxide/carbon nanotubes-COOH hybrid and their application for sensitive detection of hydrazine.  Electrochim Acta 174: 1096–1103.

Ensafi AA, Ahmadi N, Rezaei B, Mokhtari AM (2015) A new electrochemical sensor for the simultaneous determination of acetaminophen and codeine based on porous silicon/palladium nanostructure. Talanta 134:45-753.

Fang B, Feng Y, Wang G, Zhang C, Gu A, Liu M (2011) A uric acid sensor based on electrodeposition of nickel hexacyanoferrate nanoparticles on an electrode modified with multiwalled carbon nanotubes. Microchim Acta 173: 27-32.

Fashedemi OO, Ozoemena KI (2011) A facile approach to the synthesis of hydrophobic iron tetrasulfophthalocyanine (FeTSPc) nano-aggregates on multi-walled carbon nanotubes: A potential electrocatalyst for the detection of dopamine. Sens Actuators B chem 160 : 7-14.

Gholivand MB, Khodadadian M, Omidi M (2013) Electrocatalytic behavior of hybrid cobalt–manganese hexacyanoferrate film on glassy carbon electrode.  Mater Sci Eng C, 33: 774–781.

Giuseppe Egidio D B, Daniela F, Antonio P, Cosimino M,Giuseppe N, Dario D L, Francesco DN, Velia LP (2014) A rapid and simple method for the determination of 3,4-dihydroxyphenylacetic acid, norepinephrine, dopamine, and serotonin in mouse brain homogenate by HPLC with fluorimetric detection. J Pharm Biomed Anal 98: 266–270.

Gottas A, Ripel A, Boix F, Vindenes V, Mørland J, Øiestad EL (2015) Determination of dopamine concentrations in brain extracellular fluid using microdialysis with short sampling intervals, analyzed by ultrahigh performance liquid chromatography tandem mass spectrometry. J Pharmacol Toxicol Methods 74:75–79.

Habibi B, Abazari M, Pournaghi-Azar MH(2014) Simultaneous determination of codeine and caffeine using single-walled carbon nanotubes modified carbon-ceramic electrode. Colloid Surf B 114:89–95.

Hai-Bo W, Hong-Ding Z, Ying C, Ke-Jing H, Yan-Ming L A(2015) label-free and ultrasensitive fluorescent sensor for dopamine detection based on double-stranded DNA templated copper nanoparticles.  Sens Actuators B Chem 220:146–153

Heli H, Eskandari I, Sattarahmady N, Moosavi-Movahedie AA (2012) Cobalt nanoflowers: Synthesis, characterization and derivatization to cobalt hexacyanoferrate—Electrocatalytic oxidation and determination of sulfite and nitrite. Electrochim Acta 77:294– 301.

Hong SF, Chen LC (2010) A red-to-gray poly(3-methylthiophene) electrochromic device using a zinc hexacyanoferrate/PEDOT:PSS composite counter electrode. Electrochim Acta 55: 3966–3973.

Jayalakshmi M, Scholz F (2000) Performance characteristics of zinc hexacyanoferrate/Prussian blue and copper hexacyanoferrate/Prussian blue solid state secondary cells.  J Power Sources 91:217–223.

Jia Z, Wang B, Wang Y (2015) Copper hexacyanoferrate with a well-defined open framework as a positive electrode for aqueous zinc ion batteries. ‎Mater Chem Phys, 149-150:601-606.

Kao SY, Lin YS, Chin K, Hu CW, Leung MK, Ho KC (2014) High contrast and low-driving voltage electrochromic device containing triphenylamine dendritic polymer and zinc hexacyanoferrate. Sol Energy Mater Sol Cells 125 :261–267.

Karnjanakom S, Ma Y, Guan G, Phanthong P, Hao X, Du X, Samart C, Abudula A (2014) Fabrication of nickel hexacyanoferrate film on carbon fibers by unipolar pulse electrodeposition method for electrochemically switched ion exchange application Electrochim Acta 139: 36–41.

Liao HY, Liao TC, Chen WH, Chang CH, Chen LC (2016) Molybdatehexacyanoferrate (MoOHCF) thin film: A brownish red Prussian blue analog for electrochromic window application. ‎Sol Energy Mater Sol Cells, 145:8–15.

Lin L, Ning X, Jing-Jing M, Bin-Bin Z, Su-Juan L (2016) An electrochemical aptasensor for sensitive and selective detection of dopamine based on signal amplification of electrochemical-chemical redox cycling. J Electroanal Chem 775:58–63.

Li YF, Li KJ, Song G, Liu J, Zhang K, Ye BX (2013) Electrochemical behavior of codeine and its sensitive determination on graphene-based modified electrode. Sens Actuators B Chem 182:401–407.

Manasa G, Ronald JM, Ashis K S, Basavanakote MB, Sriram K, n electrochemical Bisphenol F (2018)sensor based on ZnO/G nano composite and CTAB surface modified carbon paste electrode architecture. Colloids Surf B Biointerfaces 170: 144-151

Maofang H, Chaozhan W, Yinmao W (2016) selective enrichment and determination of monoamine neurotransmitters by CU(II) immobilized magnetic solid phase extraction coupled with high-performance liquid chromatography-fluorescence detection.  Talanta, 147:437-444.

Mashadizadeh MH, Abdollahi G, Yousefi T (2016) SmHCF/multiwalled carbon nanotube modified glassy carbon electrode for the determination of codeine. J Electroanal Chem 780: 68–74.

Mashhadizadeh MH, Rasouli F (2014) Design of a New Carbon Paste Electrode Modified with TiO2 Nanoparticles to Use in an Electrochemical Study of Codeine and Simultaneous Determination of Codeine and Acetaminophen in Human Plasma Serum Samples. electroanalysis, 26:2033-2042.

Mashhadizadeh MH, Yousefi T, Ahmad Nozad G (2012) A nickel hexacyanoferrate and poly(1-naphthol) hybrid film modified electrode used in the selective electroanalysis of dopamine. Electrochim Acta 59: 321– 328.

Mazloum-Ardakan M, Beitollahi H, Amini MK, Mirkhala F, Mirjalili F (2011) A highly sensitive nanostructure-based electrochemical sensor for electrocatalytic determination of norepinephrine in the presence of acetaminophen and tryptophan. Biosens.Bioelectron, 26:2102-2106.

Na W, Xian-En Z, Shuyun Z, Yongrui H, Longfang Z, Guang C, Jinmao Y, Shu, Zhiqiang L. (2016) Determination of dopamine, serotonin, biosynthesis precursors and metabolites in rat brain microdialysates by ultrasonic-assisted in situ derivatization–dispersive liquid–liquid microextraction coupled with UHPLC-MS/MS Talanta 161: 253–264.

Noroozifar M, Khorasani-Motlagh M, Taheri A (2010)Preparation of silver hexacyanoferrate nanoparticles and its application for the simultaneous determination of ascorbic acid, dopamine and uric acid. Talanta 80:1657–1664.

Padigi P, Goncher G, Evans D, Solanki R (2015) Potassium barium hexacyanoferrate – A potential cathode material for rechargeable calcium ion batteries. J Power Sources 273:460-464

Palanisamy S, Ku S, Chen SM (2013) Dopamine sensor based on a glassy carbon electrode modified with a reduced graphene oxide and palladium nanoparticles composite. Microchim Acta 180:1037–1042.

Ponnusamy VK, Mani V, Chen SM, Huang WT, Jen JF(2014) Rapid microwave assisted synthesis of graphene nanosheets/polyethyleneimine/gold nanoparticle composite and its application to the selective electrochemical determination of dopamine. Talanta 120:148–157.

Pournaghi-Azar MH, Saadatirad A (2010) Simultaneous Determination of Paracetamol, Ascorbic Acid and Codeine by Differential Pulse Voltammetry on the Aluminum Electrode Modified by Thin Layer of Palladium. Electroanalysis 22:1592–1598.

Qiu-Mei F, Meng C Chuan-Guo S, Ning B, Hai-Ying G(2015)Integrated paper-based      electroanalytical devices for determination of dopamine extracted from striatum of rat. Sens Actuators B Chem B 209: 870–876.

Qi S, Zhao B, Tang H, Jiang X. (2015) Determination of ascorbic acid, dopamine, and uric acid by a novel electrochemical sensor based on pristine graphene. Electrochim acta 161:395-402.

Rajkumar M, Devadas B, Chen SM (2013) Electrochemical synthesis of dysprosium hexacyanoferrate micro stars incorporated multi walled carbon nanotubes and its electrocatalytic applications. Electrochim Acta105: 439–446.

Ren X, Chen C, Najatsu M, Wang X, (2011) Carbon nanotubes as adsorbents in environmental pollution management: A review Chem Eng J, 170:395–410.

Rezaei B, Mirahmadi Zare SZ (2008) Modified glassy carbon electrode with multiwall carbon nanotubes as a voltammetric sensor for determination of noscapine in biological and pharmaceutical samples. Sens Actuators B Chem 134: 292–299.

Sattarahmady N, Heli H, Moradi SE (2013)Cobalt hexacyanoferrate/graphene nanocomposite – Application for the electrocatalytic oxidation and amperometric determination of captopril.  Sens Actuators B Chem 177: 1098– 1106.

Shahrokhian S, Ghalkhani M, Adeli M, Amini MK (2009) Multi-walled carbon nanotubes with immobilised cobalt nanoparticle for modification of glassy carbon electrode: Application to sensitive voltammetric determination of thioridazine. Biosens Bioelectron 24:3235–3241

Sheetal P, Niranjan R, Soumyo M,  Ramgopal RV (2017)PVA modified ZnO nanowire based microsensors platform for relative humidity and soil moisture measurement. Sens Actuators B Chem  253: 1071-1078

Stela P, Alexandru R B, Florina P, Crina S, Maria, Marcela C R, Fumiya W, Alexandru BirisS (2015)The influence of uric and ascorbic acid on the electrochemical detection of dopamine using graphene-modified electrodes. Electrochim Acta 154:197–204.

Svorc L, Sochr J, Svítková J, Rievaj M, Bustin D (2013) Rapid and sensitive electrochemical determination of codeine in pharmaceutical formulations and human urine using a boron-doped diamond film electrode. Electrochim Acta 87: 503-510.

 

Tootoonchi A, Davarani S. S. H, Sedghi R, Shaabani A, Moazami H. R (2018) A non-enzymatic biosensor based on Pd decorated reduced graphene oxide poly (2-anilinoethanol) nanocomposite and its application for the determination of dopamine, J. Electrochem. Soc., 165 : B 150

Venkatesan S, SridharT.M., Raman S, (2021) Development of an Electrochemical Biosensor         for Determination of Dopamine by Gold Modified Poly(thiophene-3-boronic acid)- Polyphenol Oxidase Modified Electrode, Materials Letters, 130387 in press.

Vinu Mohan AM, Rambabu G, Aswini KK, Biju VM (2014)Electrocatalytic behaviour of hybrid cobalt–manganese hexacyanoferrate film on glassy carbon electrode  Thin Solid Films 565: 207-214.

Wu P, Lu S, Cai C (2004) Electrochemical preparation and characterization of a samarium hexacyanoferrate modified electrode J. Electroanal. Chem. 569:143-150.

Xu H, Xiao J, Yan L, Zhu L, Liu B (2016) An electrochemical sensor for selective detection of dopamine based on nickel tetrasulfonated phthalocyanine functionalized nitrogen-doped graphene nanocomposites. J Electroanal Chem 779:92–98.

Yongrui H, Xian-En Z, Shuyun Z, Na W, Jing S, Yubi Z, Shu L, Zhiqiang L, Guang C, Yourui S Jinmao Y(2016) n situ derivatization-ultrasound-assisted dispersive liquid–liquid microextraction for the determination of neurotransmitters in Parkinson’s rat brain microdialysates by ultrahigh performance liquid chromatography-tandem mass spectrometry.  J Chromatogr A, 1458: 70–81.

Yu L, Yuanjie X, Yu Q (2014)Polymeric membrane sensors with boronic acid functionalized boron dipyrromethene for selective measurement of dopamine  Sens Actuators B Chem 191:227– 232.

Yumin L, KunX, LiqunY, GenquanL, ZhiwenL, JunbaoH(2015)Gold-nanoparticle-based colorimetric array for detection of dopamine in urine and serum. Talanta 139:89–95.

Yunsha Z, Shulin Z, Junming H, Fanggui Y(2011)Quantum dot-enhanced chemiluminescence detection for simultaneous determination of dopamine and epinephrine by capillary electrophoresis. Talanta, 85: 2650– 2654.

Zhang Z, Yang X, Fu Y, Du K. (2015) Ultrathin molybdenum diselenide nanosheets anchored on multi-walled carbon nanotubes as anode composites for high performance sodium-ion batteries. J Power Sources 296: 2-9.

Zorione H, Fernando M, Eva B (2014)Electrochemical detection of dopamine using streptavidin-coated magnetic particles and carbon nanotube wiring.  Sens Actuators B Chem, 203: 891–898

 

 

 

 

 

---