Development of non-enzymatic glucose electrode based on Au nanoparticles decorated single-walled carbon nanohorns

doi:10.21203/rs.3.rs-198395/v1

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Development of non-enzymatic glucose electrode based on Au nanoparticles decorated single-walled carbon nanohorns

https://doi.org/10.21203/rs.3.rs-198395/v1

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published 19 Apr, 2021

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A composite with gold nanoparticles (AuNPs) decorating single-walled carbon nano-horns (SWCNHs) is synthesized and used to modify a gold electrode for non-enzymatic glucose detection. The composite was synthesized by a simple covalent bonding method. The AuNPs with an average particle size of 40 nm are dispersed homogeneously on the surface of the SWCNHs. Therefore, the synergistic effect of the AuNPs and the SWCNHs leads to an excellent glucose sensing performance. The glucose sensing tests indicate that the electrode fabricated has a linear response in the 0.5-2 mM and 4–12 mM glucose concentration range, a high sensitivity (275.33 and 352.5 µA cm^− 2 mM^− 1), and a low detection limit (0.72 µM) (S/N = 3) at + 0.3 V, as well as strong resistance to the interference by ascorbic acid (AA), uric acid (UA), dopamine (DA), galactose, and lactose. When the electrode was used for the detection of glucose in blood samples, the glucose contents detected by the electrode was in right agreement with real. The performance level reached makes the electrode a potential alternative tool for the detection of glucose.

Electronic Materials and Devices

Electrical Engineering

Gold nanoparticles

Single-walled carbon nano-horns

Non-enzymatic glucose detection

High sensitivity

Diabetes mellitus is a metabolic disorder characterized by elevated levels of blood glucose. The number of people with diabetes mellitus is increasing every year. In 2017, the International Diabetes Federation (IDF) estimated that 1 in 11 adults aged 20–79 years (451 million adults) had diabetes mellitus globally and that the number would increase to 693 million in 2045 [1]. According to the IDF, approximately 5 million deaths worldwide were related to diabetes in the 20–99 years age range in 2017, which accounts for 9.9% of the global mortality for people in this age range [2]. Therefore, the detection and monitoring of the glucose levels is essential for the prevention, the diagnosis, and the treatment of diabetes. Many glucose sensors were developed using enzymes to obtain a high sensitivity and good selectivity [3]. However, the sensitivity, the selectivity, and the stability of enzyme-based glucose sensors largely depend on the activity of the enzymes. The pH, the humidity, and the temperature influence the activity of glucose enzymes [4].

To overcome these issues, non-enzymatic glucose sensors have been developed as alternatives [5–8]. Overall, non-enzymatic glucose sensors have many strong advantages, such as a high reproducibility, a high stability, and structural simplicity. To date, many noble metals (Pt, Au, and Pd), transition metals (Cu, Ni, and Co) and their oxides or hydroxides have been used in non-enzymatic glucose sensors [9–15]. Among them, Au is widely used because it produces a high glucose oxidation current in neutral or alkaline conditions [16, 17]. Furthermore, Au nanoparticles (AuNPs) are glucose catalysts that have attracted much attention because of their large surface area, their excellent catalytic activity, and a high resistance to toxic Cl⁻ [18]. In addition, the favorable structure of the carrier-catalyst composite is a major advantage for sensors [19–21]. The carrier can affect the dispersion of the catalyst, enhance the conductivity and the stability of the material, and make the catalyst work more effectively. Single-walled carbon nano-horns (SWCNHs) are a nanostructured carbon material with horn-shaped sheaths composed of graphene sheets and has a conical structure with a particularly sharp apical angle [22]. Their excellent electrical conductivity, their high specific surface area, and the vast internal space of the SWCNHs make it an excellent carrier for other particles. Moreover, SWCNHs are produced without using any metal catalyst at a high purity and can be used directly without further purification [23].

Considering the many merits of AuNPs and SWCNHs, we first developed an Au electrode modified with an AuNPs and SWCNHs composite for the detection of glucose. Covalent bonding is used in the preparation of the Au-SWCNHs composite. The method is simple and has a low cost. Additionally, it avoids the use of toxic reagents and the composite performs very well for the electrochemical detection of glucose. SWCNHs have a large surface area and good electrochemical properties [22], which gives the composite prepared a stable structure and a high catalytic activity for glucose. There are enough binding sites for the gold nanoparticles on the modified SWCNHs to enable the formation of s-Au bond. Glucose sensing tests confirmed that the fabricated electrode had high sensitivity, good stability, anti-interference and reproducibility, which is used as the basis for developing the glucose sensor.

2.1 Chemicals and apparatus

The SWCNHs were purchased from XFNANO Materials Tech Co., Ltd. Nitric acid (HNO₃), sulfuric acid (H₂SO₄), cysteamine hydrochloride (C₂H₇NS·HCl), chloroauric acid (HAuCl₄), sodium citrate (Na₃C₆H₅O₇), sodium hydrate (NaOH), uric acid (UA), dopamine (DA), ascorbic acid (AA), d-(+)-galactose, lactose, sucrose, and DL-lactic acid were purchased from Sigma-Aldrich. All the chemicals used in this work were of analytical grade and used without further purification.

Scanning electron microscopy (SEM) images were recorded on a JSM-IT300 (JEOL, Ltd., Japan). We used a Renishaw InVia confocal Raman system (Talos F200S, Thermo Fisher Scientific, United States) to examine the defects in the samples. All the electrochemical experiments were performed on a CS2350 electrochemical workstation (Corrtest Instruments Corp., Ltd., Wuhan, China).

2.2 Preparation of the Au-SWCNHs composite

The composite comprised of AuNPs decorating SWCNHs was synthesized by a three-step method. First, oxidized SWCNHs (oxSWCNHs) were prepared via a modified Hummers method [24]. We initially mixed 5 ml H₂SO₄ (98%) and 15 ml HNO₃ (62%). Next, 30 mg SWCNHs were treated with the mixed acid for 16 h under continuous stirring at 50℃ through a hydrothermal reaction. The oxSWCNHs were collected by centrifugation at 12000 rpm for 5 min. Then, the supernatant was removed, and deionized water was added to disperse the oxSWCNHs for further centrifugation. We carried out several rounds of centrifugation and dispersion until the supernatant was neutral. Finally, the oxSWCNHs collected were dried in an oven at 90 ℃. Then, the oxSWCNHs were dispersed into 30 ml of deionized water, and 50 mg of C₂H₇NS·HCl were added to the dispersion. The mixture was treated at 90℃ for 24 h with continuous agitation. The mixture obtained was centrifuged at 12000 rpm and washed with deionized water several times. After centrifugation, the composites were placed into deionized water to form a suspended solution, and 5 ml of an HAuCl₄ solution (0.01 M) were added. The mixture was sonicated for 30 min to promote the interaction between the gold ions and the sulfhydryl (-SH) groups of the oxSWCNHs. The mixture was heated to 90 ℃ and 10 ml of a 4% Na₃C₆H₅O₇ solution were added. The mixed solution was stirred for 30 min until Au⁺ was reduced to Au nanoparticles. The dispersion obtained was then centrifuged, washed several times with deionized water, and dried at 90 ℃. The nanocomposite obtained was named Au-SWCNHs. Finally, the Au-SWCNHs black powder was collected and stored at 4 ℃ for further use.

2.3 Preparation of the Au-SWCNHs modified Au electrode

Before its modification, the Au electrode was polished, washed several times with deionized water and anhydrous ethanol under sonication, and dried in a nitrogen stream. First, we added 10 mg of the Au-SWCNHs powder prepared into 5 ml of anhydrous ethanol and sonicated the mixture for 20 min to obtain an Au-SWCNHs ethanol suspension at 2 mg ml^− 1. Then, we dropped 5 µL of the Au-SWCNHs ethanol suspension on the Au electrode and let it dry naturally to obtain the Au-SWCNHs/Au electrode (Au-SWCNHs/Au). The electrode was stored at 4 ℃ for further use.

3.1. Preparation and characterization of the Au-SWCNHs composites

Figure 1 illustrates the preparation of the Au-SWCNHs composite. First, the SWCNHs were treated with mixed acid (H₂SO₄/HNO₃). Upon oxidation, oxygen-containing groups like carboxyl groups (-COOH) were generated on the surface of the SWCNHs. Subsequently, the C₂H₇NS·HCl added was ionized in water to produce positively charged sulfur-containing ions while the oxygen-containing groups on the surface of the oxSWCNHs ionized were deprotonated and became negatively charged. Both positively and negatively charged ions were then combined by electrostatic forces. After the addition of HAuCl₄, it was dispersed by sonication and fully mixed with the SWCNHs, H⁺ of -SH was replaced by Au³⁺. Finally, AuNPs were formed when Au³⁺ was reduced by Na₃C₆H₅O₇. Fig. S1 in the Supplementary information shows the Raman spectra of the SWCNHs and oxSWCNHs samples. The D band (1334 cm^− 1) and the G band (1564 cm^− 1) of both samples were detected. The intensity ratio of D and G peaks (I_D/I_G) is an indicator of the level of defects [25]. The oxSWCNHs (1.24) have a higher I_D/I_G ratio than the original SWCNH (0.53). This indicates the structural deformation of the functional SWCNHs by combing functional groups. The unmodified surface of the SWCNH is inert and does not promote the chemical synthesis of surface materials. Therefore, a surface modification is required to introduce functional groups to provide a large number of chemically active binding sites for the modification by other materials. The functional groups on the surface of the SWCNHs provided binding sites for C₂H₇NS·HCl and enabled the further modification with the AuNPs.

Figure 2 shows the SEM images of the SWCNHs and Au-SWCNHs samples. Figure 2a and 2b compares the Au nanoparticles dispersed on the surface of the SWCNHs. Figure 2c shows that several isolated Au nanoparticles were scattered on the SWCNHs surface and most Au nanoparticles were spaced by 40–60 nm, indicating that the Au nanoparticles are well distributed on the SWCNH surface. These spherical Au nanoparticles have a considerably large surface area. They are tightly bound to the surface of the SWCNHs and are evenly dispersed. This structure provides a large number of AuNPs as the electrocatalyst.

Figure 3a and 3b respectively show the elemental composition of oxSWCNHs and Au-SWCNHs determined by energy dispersive spectroscopy (EDS). The modification of the Au nanoparticles clearly leads to the reduction of the oxygen atoms, which is consistent with other results in the literature [26]. When comparing the different samples, the N content was higher in the samples with a higher Au content. This is because the AuNPs modification occurs spontaneously with the formation of an Au-S bond, which binds to the oxSWCNHs via the N-containing C₂H₇NS·HCl. The AuNPs were successfully synthesized by chemical bonding to the SWCNHs and are expected to have good surface properties in electrochemical sensors.

3.2. Electrochemical characterization of the Au-SWCNHs/Au eletrode

A three-electrode cell was used for the electrochemical measurements. It contained a platinum counter electrode, an Ag/AgCl reference electrode, and the modified electrodes as the working electrode. The electrochemical behavior of the Au-SWCNHs/Au electrode and the bare Au electrode was first studied by cyclic voltammetry (CV). Figure 4a shows the cyclic voltammograms obtained for the Au-SWCNHs/Au electrode and the Au electrode in a 1.0 M H₂SO₄ solution. A wide anodic peak appeared at 1.1 V for the Au-SWCNHs /Au electrode. It corresponds to the formation of gold oxide (Au₂O₃). Additionally, a cathodic peak was observed at 0.87 V due to the reduction of the gold oxide. The blue line in Fig. 5a shows that both redox peaks had the same direction as the red line. The value of the peak current of the Au-SWCNHs/Au electrode was significantly larger than that for the bare Au electrode, which indicated that the surface area of the Au-SWCNHs/Au electrode was larger than that of the bare Au electrode. The larger surface area is due to the unique dispersion of AuNPs on the SWCNHs surface that provides more reactive sites for the redox reaction and the electrocatalytic activity.

Then, we compared the electrochemical glucose sensing with the Au-SWCNHs/Au electrode to that of the bare Au electrode by cyclic voltammetry in a 0.1 M NaOH solution without and with glucose at a scan rate of 20 mV s^− 1. Figure 3b shows the CV response of the Au-SWCNHs/Au electrode. In the absence of glucose (black curve), we observed an anodic oxidation peak from the oxidization of Au to Au₂O₃ and a cathodic peak from the reduction of Au₂O₃ [27] on the Au-SWCNHs/Au electrode. After the addition of the glucose, the CV of Au-SWCNHs/Au electrode was significantly altered and a series of complex electrochemical processes took place. During the forward scanning, two new oxidation peaks were observed at -0.3 V (peak 1) and at + 0.52 V (peak 2). Peak 1corresponds to the direct electrochemical oxidation of glucose to gluconolactone. Then, gluconolactone was further oxidized to produce peak 2. The AuOH site is considered as the active site for glucose oxidation and the oxidation of glucose on Au depends largely on the number of AuOH sites available [28]. Usually, the OH⁻ ions in the NaOH solution adsorb onto the surface of the gold at a certain potential to form an active site. At the low potential of peak 1, the amount of AuOH is very limited and the oxidation of glucose is incomplete. When the potential increases, the amount of AuOH increases and gluconolactone is further oxidized (peak 2). An excessively high potential ( > + 0.52 V) leads to the formation of Au₂O₃ and the reduction of the AuOH active site, which terminates the oxidation of gluconolactone. In the reverse scanning, Au₂O₃ is reduced and AuOH is regenerated to promote glucose oxidation and a significant anodic peak (peak 3) appears at + 0.2 V. All the peak currents increase with the increasing of concentrations of the glucose, which indicated the Au-SWCNHs/Au electrode is sensitive to the glucose. Figure 3c shows the CV response of the bare Au electrode. Though the curves of the bare electrode are similar with those of Au-SWCNHs/Au electrode, the peak currents of the bare electrode are lower than those of Au-SWCNHs/Au electrode. It indicates that the modification of the Au-SWCNHs composite material significantly improves its catalytic activity for the oxidation of glucose.

Figure 4d shows the CV response of the bare Au electrode and the Au-SWCNHs/Au electrode in a 0.1 M NaOH solution with 8 mM glucose. The current at the Au-SWCNHs/Au electrode was generally higher and a significant peak at + 0.52 V appeared. This indicated that the Au-SWCNHs significantly improved the sensitivity to glucose and further improved the electrochemical performance of the non-enzymatic glucose sensing approach used. Overall, the synergistic effect of the AuNPs and the SWCNHs improves the performance of the detection of glucose.

To determine the voltage at which the continuous injection of glucose must be conducted, the amperometric reaction of the Au-SWCNHs/Au electrode to the addition of 4 mM glucose at different voltages was studied in a 0.1 M NaOH solution (Fig. S2). The electrode had the maximum response at + 0.3 V, which was therefore selected for the subsequent experiments.

To determine the dependence of the electrochemical signals on the glucose concentration, the amperometric reaction of the Au-SWCNH/Au electrode to the continuous injection of glucose was studied at a potential of + 0.3 V in 0.1 M NaOH. Figure 5a shows the corresponding current-time (i-t) curve. The intensity of the current at the electrode increased with the addition of glucose. Figure 5b shows the calibration curve, and both linear ranges with slopes of 413 µA mM^− 1 cm^− 2 and 528.75 µA mM^− 1 cm^− 2, respectively. The sensitivity in the first and second linear range was 275.33 µA mM^− 1 cm^− 2 and 352.5 µA mM^− 1 cm^− 2, respectively. The limit of detection (LOD) was determined experimentally at 0.72 µM with a signal-to-noise ratio (S/N) of 3. Table 1 compares the electrochemical performances of the Au-SWCNHs/Au electrode with other non-enzymatic glucose sensors using AuNPs. The developed electrode had a wider linear concentration range and a higher sensitivity than those of in most of cited reports. The unique structure of Au-SWCNHs creating a large surface area and abundant active sites makes glucose easily migrate to the electrode surface for a high sensitivity.

3.3. Selectivity, stability, and reproducibility of the Au-SWCNHs/Au electrodes

To evaluate the selectivity of the Au-SWCNHs/Au electrode, we examined the effects of interfering substances like ascorbic acid (AA), uric acid (UA), dopamine (DA), galactose, lactose, sucrose, which typically coexist with glucose in human serum [29]. Therefore, we tested the Au-SWCNHs/Au electrode in a solution where the molar ratio of glucose to each interfering substance was 10:1. Figure 6 shows that the change in the current was insignificant in the presence of interfering substances while the current was significant with the increment of the glucose. This indicated that Au-SWCNHs/Au electrode has excellent selectivity towards glucose. For the stability study, we determined that the current response remained at 90.4% and 78.3% of the maximum value for 600 s and 2000 s, respectively (Fig. S3). The Au-SWCNHs/Au electrodes were stored in an airtight container at room temperature for 19 days and the current response to 4 mM glucose was checked every other day (Fig. S4). After 15 days of storage, the current response only decreased by 8.6%. To study the influence of environmental variables such as humidity, the fabricated electrode was exposed to air for 3 days and tested under similar conditions. The current response remained around 89%. To evaluate the reproducibility, we prepared five electrodes by the same method and used them to detect 4 mM glucose. The relative standard deviation (RSDs) of the glucose response was less than 8.7%. Overall, our results demonstrated that the Au-SWCNHs/Au electrode had an excellent selectivity towards glucose, a good long-term stability, and good reproducibility.

3.4. Real sample analysis

The feasibility of the Au-SWCNHs/Au electrode in the practical application was performed by testing the glucose in human blood serum. The tests were conducted in 0.1 M NaOH solution with 100 µL serum added and the sensing results are shown in Table 2. Glucose was added to human serum with and without glucose continuously, and the detection recovery was 93.50-97.67%. This indicated that Au-SWCNHs/Au electrode here reported can be potentially utilized for the real sample analysis.

AuNPs with an average particle size of 40 nm were synthesized on SWCNHs using an effective method to produce a stable chemical bond. The nanocomposite-modified electrode had a high sensitivity, a wide linear response, good selectivity, a high stability, and a high reproducibility. The AuNPs and the unique structure of the SWCNHs significantly enhanced the catalytic activity of the electrode for glucose. The stable chemical bond between them greatly improved the performance and the storage of the glucose electrode. The large surface area of the microstructure of the SWCNHs provides a good basis to bind a large number of AuNPs, thereby effectively preventing aggregation and deactivation. Moreover, the excellent conductivity of the SWCNHs results in a faster electron transfer between the Au-SWCNHs composite and the Au electrode. Meanwhile, due to the significant catalytic activity of the Au-SWCNHs/Au electrode in the low concentration range of glucose, the electrode has great potential for the detection of glucose in sweat. We believe that our work opens a new route for the preparation of Au-SWCNHs composites and sets an example for the production of high-quality nanomaterials for sensing applications.

Acknowledgements

The authors thank to partly financial support from the National Natural Science Foundation of China (No. 61704035), Natural Science Foundation of Guangxi Province (2017GXNSFBA198125), Guangxi technology projects (AD19110076, AD19110063).

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Table1

Comparison of the Au-SWCNHs/Au electrode with other non-enzymatic glucose electrodes.

Electrode matrix	Linear range (mM)	Sensitivity (μA mM^-1 cm^-2)	Detection limit(mM)	Linear range (mM)	Sensitivity (μA mM^-1 cm^-2)	Ref.
AuNPfilm/FTO glass	0.01-10	10.65	2	-	-	25
AuNPfilm/ITO glass	0-11	23	5	-	-	30
Au NPs/GONR/CS	0.005-4.92	59.1	5	4.92-10	31.4	19
AuNPs-MWCNTs-CS cryogel/AuE	0.001-1	27.7	0.5	-	-	31
AuNP/PANI/GCE	0.001-1	27.7	500	-	-	32
AuNP/PANI/CC	0.01026-10	150	3.08	-	-	33
Au-SWCNHs/Au	0.5-2	275.33	0.72	4-12	352.5	This work

AuNp: gold nanoparticle; FTO: fluorine-doped tin oxide; ITO: indium tin oxide; GONR: Graphene Oxide Nanoribbon; CS: Chitosan; AuE: Au electrode; MWCNTs: multi-walled carbon nanotubes; PANI: polyaniline; GCE: glass carbon electrode; CC: carbon cloth; SWCNHs: single-walled carbon nanohorns

Table 2

The detection of glucose in human serum by the Au-SWCNHs/Au electrode.

Sample	Original(mM)	Added(mM)	Found(mM)	Recovery(%)
Sample 1	0	1	0.97	97.00
	0	2	1.92	96.00
	0	3	2.93	97.67
Sample 2	1	1	1.87	93.50
	1	2	2.82	94.00

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published 19 Apr, 2021

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Development of non-enzymatic glucose electrode based on Au nanoparticles decorated single-walled carbon nanohorns

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Abstract

Figures

1. Introduction

2. Materials And Methods

2.1 Chemicals and apparatus

2.2 Preparation of the Au-SWCNHs composite

2.3 Preparation of the Au-SWCNHs modified Au electrode

3. Results And Discussion

3.1. Preparation and characterization of the Au-SWCNHs composites

3.2. Electrochemical characterization of the Au-SWCNHs/Au eletrode

3.3. Selectivity, stability, and reproducibility of the Au-SWCNHs/Au electrodes

3.4. Real sample analysis

4. Conclusion

Declarations

Acknowledgements

References

Tables

Supplementary Files

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Journal Publication

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