A functional electrochemical sensing platform for the detection of lead ions

doi:10.21203/rs.3.rs-2449601/v1

A novel electrochemical sensor for the detection of lead ions was constructed by using electrodeposition of gold nanoparticles (GNPs) and glutathione (GSH) onto reduced graphene oxide (rGO) to form a GSH@GNP@rGO nanocomposite on a glassy carbon electrode (GSH@GNP@rGO@GCE). The sensing properties of the obtained sensor were tested by Cyclic Voltammetry (CV) and Differential Pulse Voltammetry (DPV). Under optimized experimental conditions, the voltammetry response gradually raises by increasing the concentration (2-20 μΜ). The result showed that the GSH@GNP@rGO@GCE sensor exhibited high sensitivity towards Pb(II) with a low detection limit of 0.43 μMby DPV. Our studies suggest that the GSH@GNP@rGO nanocomposite could potentially be used for detecting Pb(II).

electrochemical sensor

lead ions

graphene

gold nanoparticle

glutathione

Environmental pollution of heavy metals has become of great concern today with the increase in industrialization and technological developments. [1, 2] Heavy metal toxicity is known to be a serious threat to health by spreading from many sources such as industrial activities [3], various urban wastes [4], mining [5], use of fertilizers [6] and pesticides in agriculture [7], exhaust gases of motor vehicles. [8] Due to their high toxicity, lead, arsenic, cadmium, chromium, and mercury are among the heavy metals that pose a danger to public health. [9, 10] Even low exposure to these metals is known to cause multiple organ damage. [11] Among these heavy metals, lead is a highly toxic element that especially affects the central nervous system and then the brain. [12, 13] Children are at greater risk than adults for the neurotoxic effects of lead. [14] Although most of the lead is stored in the bones, it can also pass into the brain, the fetus in the womb, and breast milk. [15] The studies showed that various neurological problems such as Parkinson's disease, schizophrenia, some behavioral problems, Alzheimer's disease, and mental retardation occur due to excess lead in the body. [16] Because of the high toxicity of heavy metals on the ecosystem, many studies are currently being conducted on the determination [17–19] and removal of these metals by using different voltammetric techniques [20–22]. Also, traditional analytical methods such as atomic absorption spectroscopy [23], fluorescence spectrometry [24], and atomic emission spectroscopy [25], can be used for this purpose. If electrochemical and conventional analytical methods are compared electrochemical methods give more effective results in a shorter time with simpler procedures For this reason, the use of electrochemical methods instead of the existing conventional physical and chemical processes for the detection of heavy metals is quite effective. [26–28] Graphene and its derivatives have attracted a great deal of interest in electrochemical sensors because of its electrocatalytic activity, electrical conductivity, biocompatibility, and versatile surface modification. [29–31] Also gold nanoparticles (GNPs) are extensively used for the fabrication of new sensors due to their biocompatibility, exceptional electronic properties, and conductivity. [32, 33] Today, the method of deposition of various metallic structures such as gold, platinum, and silver on the electrode surface is used quite frequently to increase the sensitivity of electrochemical detection[34, 35]. In addition, many small molecules are used as immobilization matrices for the production of electrochemical sensors, as they can selectively bind to the target site through their active functional groups and form a stable structure. [36, 37] GSH is a thiolated tripeptide with multiple abundant active sites for binding analytes. Owing to these advantages, electrochemical sensors containing GSH-functionalized gold nanoparticles and reduced graphene have been developed for the detection of histamine [38], nitric oxide [39], bisphenol A [40], tryptophan [41], and metal ions [42]. However, there is no paper published about the electrochemical detection of Pb(II) ions by using this nanocomposite.

In this study, a nanocomposite containing rGO, GNP, and GSH was modified to the glassy carbon electrode (GCE) surface to determine Pb(II) ions by electrochemical methods. The electrodes were primarily modified using electrochemical reduction of graphene oxide (GO), then electrodeposition of gold nanoparticles on this modified surface according to the literature methods [43]. Lastly, GSH was polymerized on this surface to form a stable nanocomposite modified electrode (GSH@GNP@rGO@GCE). Using the GSH@GNP@rGO@GCE electrode, the determination of the Pb(II) ion was made by CV and DPV techniques. The fabricated GSH@GNP@rGO@GCE electrode shows highly attractive electrocatalytic activity towards Pb (II) detection in the aqueous medium.

2.1 Reagents

All reagents are in analytical grade and used as received. The followings were purchased from Sigma-Aldrich: hydrogen tetrachloroaurate trihydrate (HAuCl₄.3H₂O), graphite, potassium permanganate (KMnO₄), concentrated sulfuric acid (H₂SO₄), hydrogen peroxide (H₂O₂), sodium nitrate (NaNO₃), hydrochloric acid (HCl), and L-Glutathione reduced. The followings were purchased from Merck: cadmium nitrate tetrahydrate (Cd(NO₃)₂.4H₂O), potassium chloride (KCl), sodium hydroxide (NaOH), potassium nitrate (KNO₃), potassium hexacyanoferrate(II) trihydrate (K₄[Fe(CN)₆].3H₂O, lead(II) nitrate Pb(NO₃)₂ and phosphoric acid (H₃PO₄). In the electrode modification stages, phosphate buffer solution (0.1 M) was used as the electrolyte. Ultrapure water was used in all experiments.

2.2 Apparatus

UV-Vis spectra were recorded by Shimadzu UV-1700 UV–vis spectrophotometer. A Perkin-Elmer Spectrum 100 FT-IR spectrometer was used for FT-IR spectra. The morphology of nanocomposite materials was characterized using SEM (ZEISS EVO LS10). The full electrochemical analysis was performed from a single-channel potentiostat (Gamry Instruments, Model 600C Series). The working electrode was a bare glassy carbon disk (BAS Model MF-2012), the counter electrode was a Pt wire and the reference electrode was Ag/AgCl/KCl(sat.)

2.3 Synthesis of Graphene Oxide

GO was synthesized according to the literature method using synthetic graphite powder [44].

2.4 Fabrication of modified glassy carbon electrode (GSH@GNP@rGO@GCE)

Modification of the GCE with rGO and electrodeposition of GNPs on this surface was performed according to the literature method [43]. The electropolymerization of GSH was carried out in the potential range of − 1.5 to + 2.2 V through ten cycles in 0.1M PBS (pH = 6.0) at 100 mV/s. The resulting modified electrode (GSH@GNP@rGO@GCE) was then dried in air. A schematic presentation of the modified electrode surface is given in Scheme 1.

3.1 Spectral Characterization

FT-IR spectra is especially useful in identifying the different oxygen functionalities in GO [45]. In the FT-IR spectra (Fig.1a), the characteristic peaks appear for O–H stretching vibrations at 3365 cm^-1, C–H groups at 2907 cm^-1, C=O stretching mode in the carboxyl group at 1718 cm^-1, aromatic C=C bond at 1634 cm^-1, epoxy C–OH stretching peak at 1146 cm^-1, alkoxy C–O stretching band at 1035 cm^-1[46, 47]. Results revealed that GO has formed successfully.

The µ-µ* and n − π* transitions of the C = C bonds and C = O bonds in the GO structure were observed around 229 nm and 300 nm, respectively (Fig. 1b). The results obtained in the UV-Vis spectrum are in agreement with previous studies [48, 49].

3.2 Electrochemical characterization

The creation of nanocomposites on the electrode surface was carried out in three steps using the CV technique. Firstly, the surface of the GCE was modified by a drop-casting using GO. When Fig. 3a is examined, it is seen that the GO modified electrode gives a cathodic peak around − 1.2 V belongs to the reduction of oxygen functional groups [50, 51]. This peak decreased in the second cycle and completely disappeared in the third cycle (Fig. 3a).

Voltammogram of the electrodeposition of GNPs onto the rGO modified GCE surface is given in Fig. 3b. The peak of the reduction of Au ³⁺ to Au⁰ was observed at approximately − 1.10 V. GSH polymerization to the GCE electrode surface was performed with 10 cycles between 1.5 V and 2 V. The polymerization of GSH on the electrode surface started with the oxidation peaks observed at 0.32 V and 1.54 V and the reduction peaks observed at -0.43 V (Fig. 3c). The increase in the intensity of these peaks as the number of cycles increases is a sign of polymerization on the surface [52]. The CV technique was also used in the characterization of modified surfaces with a ferricyanide redox probe, and the voltammograms of 1mM [Fe(CN)₆] ^3−/4− in 0.1 M KCl solution of the electrode surfaces of GCE, rGO@GCE, GNP@rGO@GCE and GSH@GNP@rGO@GCE are given in Fig. 3d. The current and potential values of the voltammogram are given in Table 1. The redox peak potential differences for GCE, rGO@GCE, GNP@rGO@GCE, and GSH@GNP@rGO@GCE surfaces are given as ΔEp of 121.8 mV, 119.1 mV, 110.1 mV, and 109.8 mV respectively. When the GSH@GNP@rGO@GCE surface is compared with the GCE surface, it was observed that the peak current increased significantly. Table 1 gives Ipa/Ipc ratios for each surface. These values are 1.42, 1.41, 1.40, and 1.34 for the modified surfaces. The Ipa/Ipc ratio on the GSH@GNP@rGO@GCE surface shows that electron transfer is faster on this surface compared to other surfaces. All these results show that the surface area increases with the GSH modification, increasing the peak current. Therefore, we can say that GSH, GNP, and rGO modification increase the electrochemical performance of the electrode.

Table 1

Voltammetric data for 10^− 3 M [Fe(CN)₆]^3−/4 (in 0.1 M KCl) using GCE, rGO@GCE, GNP@rGO@GCE and GSH@GNP@rGO@GCE at the scan rate of 100 mV s^-1 (vs. Ag/AgCl electrode)
Surfaces	Anodic peak current Ipa, µA	Cathodic peak current Ipc, µA	Ipa/Ipc	Anodic peak potential Epa, mV	Cathodic peak potential Epc, mV	ΔEp
GCE	80.37	-56.44	1.42	517.6	395.8	121.8
rGO@GCE	91.41	-64.42	1.41	477.7	358.6	119.1
GNP@rGO@GCE	104.8	-74.69	1.40	449.4	339.3	110.1
GSH@GNP@rGO@GCE	108.9	-80.67	1.34	435.6	325.8	109.8

3.3 Electrochemical detection for heavy metal ions

CV and DPV techniques were used under optimized conditions to quantitatively analyze Pb(II), Cd(II), and Hg(II) ions. For this purpose, the GSH@GNP@rGO@GCE electrode was used as the working electrode, and the supporting electrolyte and scanning rate were optimized with the help of the CV technique using 10^-3M Pb(II) ion solutions. Experiments were made using KCl, KNO₃, HCl and H₂SO₄ as supporting electrolytes and the results are given in Fig. 4. In the selected supporting electrolytes, the maximum peak current was obtained with the HCl (Fig. 4b) But, we were unable to obtain reproducible results with this supporting electrolyte. When we used H₂SO₄, we saw that the current value was very close to zero and there was no peak (Fig. 4) Well-defined Pb (II) peaks were obtainable when using 0.1 M KCl (Fig. 4c). So this supporting electrolyte was explored in further investigations (Fig. 4c).

Voltammograms of the modified electrode (GSH@GNP@rGO@GCE) in 10^-3M Pb (II) solution were investigated at scanning rates of 25 mV s^-1, 50 mV, s^-1 and 100 mV s^-1 (Fig. 5). Since the highest current response was obtained at 100 mV s^-1, the scanning rate was chosen as 100 mV s^-1 in the studies.

To examine the usability of the obtained modified electrode in Hg(II), Pb(II), and Cd(II) determination, CV voltammograms of metal ions in 0.1 M KCl solution were performed using GSH@GNP@rGO@GCE as the working electrode. The results are detailed in Table 2. A peak is observed on the modified electrode surface for Pb ²⁺ and Cd ²⁺ metal ions whereas for the Hg(II) ion, the current response on the modified surface was higher as seen in the Fig. 6a and 6b.

Table 2. Electrochemical parameters of GSH@GNP@rGO@GCE working electrode for a) 10^-3M Pb(II) b) 10^-3M Cd(II) c) 10^-3M Hg(II) solution prepared in 0.1 M KCl at the scan rate of 100 mV s^-1 (vs. Ag/AgCl electrode)

Metal ion

Anodic peak current

I_a, µA

Cathodic peak current

I_c, µA

Anodic peak potential

Ep_a, mV

Cathodic peak potential

Ep_c, mV

Pb(II)

280.1

-26.82

1.359

1.033

Cd(II)

32.14

-4.543

1.329

0.3997

Hg(II)

20.25

-11.24

0.315

0.2071

When Table 2 is examined, it is seen that the GSH@GNP@rGO@GCE electrode surface shows the highest value of I_a (280.1 µA) in Pb (II) solution. This result shows us that the electrochemical interaction of the modified electrode with Pb(II) ions is stronger than that of Hg (II) and Cd (II) ions and this electrode surface can be used for the quantitative determination of Pb(II) ion. For this reason, detection limit of the obtained sensor was determined with the DPV technique by using different concentrations of Pb (II) solutions ranging from 2 µM to 20 µM (Fig. 7).

As shown in Fig. 7a and 7b, with increasing in metal ion concentration from 2 µM to 20 µM, the peak current increased linearly with a correlation coefficient very close to unity (R² = 0.993). The limit of detection was calculated to be 0,43 µM [53]. These results show that compared to other modified electrode surfaces, the GSH@GNP@rGO@GCE electrode is quite effective in the determination of Pb(II) ions (Table 3).

Table 3

Sensing performances of different modified surfaces for electrochemical detection of Pb(II) ions
Modified Electrode	Electrochemical technique	Limit of detection	Linear concentration range	Reference
Glu-h-ZnO/GCE	DPV	0.42 µM	2–18 µM	[54]
EDTA_PANI/SWCNTs/SS	DPV	1.65 µM	2–37 µM	[55]
FGO	SWASV	0.01 µM	0.3-5 µM	[56]
BD-NCD	LSW	1.339 µM	1-22.5	[57]
rGO/AuHCl₄/GSH/GCE	DPV	0.43 µM	2–20 µM	Currently work

3.4 Repeatability, reproducibility, long term stability of GSH@GNP@rGO@GCE

Repeatability and reproducibility of GSH@GNP@rGO@GCE were investigated in a 0.1 M KCl solution containing 10 µM Pb(II) by the DPV method. The repeatability of the GSH@GNP@rGO@GCE electrode was measured by reusing the same modified electrode in three successive measurements (Fig. 8a). Calculated RSD of 1.03% revealed good repeatability of GSH@GNP@rGO@GCE

The sensor's reproducibility experiments were carried out to see whether the GSH@GNP@rGO@GCE would yield the same result or otherwise. For the reproducibility experiments, three modified electrodes were prepared for Pb (II) determination using the same method, and the RSD value the for all three electrodes was calculated to be 0.82% indicating a satisfactory reproducibility as presented in Fig. 8b.

The stability of GSH@GNP@rGO@GCE was measured using the same sensor to detect 10 Μm Pb(II) by comparing the CV responses over 15 days. As seen in Fig. 8c, the stability of the GSH@GNP@rGO@GCE was very high, because the electrode response maintained 96. 68% of its initial current response.

3.5 Testing of the influence of Cd(II) and Hg(II) ions

The selectivity study of the obtained electrochemical sensor against Pb (II) ions was investigated in the presence of Cd(II) and Hg(II) ions. For this purpose, DPV voltammograms were obtained by adding 10 µM Cd(II) and 10 µM Hg (II) ions to the solution containing 10 µM Pb(II) (Fig. 9a). In these Pb–Cd-Hg systems, there was no peak observed for Hg(II) ions. For this reason, to understand the sensor’s selectivity against Hg (II) ions, DPV voltammograms were taken by adding 10 µM Hg (II) ions to the solution containing 10 µM Pb(II), and the result is given in Fig. 9b. When Fig. 9b is examined, it is seen that although Hg (II) ions reduce the Pb(II) current value by about 10 times, the sensor is still quite selective toward Pb(II) ions in the presence of Hg (II)

In this study, a glassy carbon electrode was modified with GSH@GNP@rGO nanocomposite through an easy and suitable modification process for sensitive and selective Pb(II) ions determination. Characterizations of synthesized materials and obtained surfaces were made using UV-Vis, FT-IR, SEM, and CV techniques. The detection limit, repeatability, reproducibility, stability, and selectivity of the GSH@GNP@rGO@GCE sensor were investigated using CV and DPV methods. The results showed that the sensor gave a linear graph between the 2 µM and 20 µM range and the detection limit was 0.43 µM. It also showed that the sensor was still stable after 15 days, and was highly selective towards Pb(II) ions in the presence of Cd(II) and Hg(II) ions. In brief, a novel sensor was constructed for the rapid, stable, selective, and sensitive determination of Pb(II) ions.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

The authors gratefully thank Research Found of Selcuk University (20201061) for the financial support.

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Scheme 1 is available in the Supplementary Files section.

No competing interests reported.

scheme1.png
Scheme 1 Schematic diagram of modification process of GCE surface

A functional electrochemical sensing platform for the detection of lead ions

Status:

Version 1

Abstract

Figures

1 Introduction

2 Materials And Methods

2.1 Reagents

2.2 Apparatus

2.3 Synthesis of Graphene Oxide

2.4 Fabrication of modified glassy carbon electrode (GSH@GNP@rGO@GCE)

3 Results And Discussion

3.1 Spectral Characterization

3.2 Electrochemical characterization

3.3 Electrochemical detection for heavy metal ions

3.4 Repeatability, reproducibility, long term stability of GSH@GNP@rGO@GCE

3.5 Testing of the influence of Cd(II) and Hg(II) ions

Conclusions

Declarations

References

Scheme

Additional Declarations

Supplementary Files

Status:

Version 1