CN108845010A - Ionic liquid auxiliary synthesis of carbon/molybdenum disulfide and graphene oxide composite material are for detecting chloramphenicol - Google Patents

Abstract

The invention provides a composite material based on ionic liquid to obtain delaminated molybdenum disulfide and graphene oxide, a modified electrode, an electrochemical sensor and the application for measuring chloramphenicol. The morphology and structure of the composite material were characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction, and the electrochemical characterization was performed by cyclic voltammetry and electrochemical impedance spectroscopy, showing good electrochemical performance and Electrocatalytic ability. The sensor has good stability, repeatability and reproducibility, and can be used for the determination of chloramphenicol in eye drops, milk and urine samples.

Description

Ionic liquid-assisted synthesis of molybdenum disulfide and graphene oxide composites for detection Chloramphenicol

technical field

The present invention relates to a novel composite material, in particular, the present invention relates to a novel composite material based on ionic liquid to obtain delaminated molybdenum disulfide and graphene oxide, as well as the application of a high-sensitivity electrochemical sensor and determination of chloramphenicol.

Background technique

Since graphene was successfully exfoliated from graphite, research on layered two-dimension (2D) nanomaterials has progressed by leaps and bounds [1]. Molybdenum disulfide (MoS ₂ ), a 2D layered nanomaterial similar to graphene, has attracted much attention due to its excellent properties in nanoelectronics, optoelectronics, catalysis and energy harvesting [2,3].

_The current methods for preparing 2D MoS mainly include mechanical dissociation, ion intercalation exfoliation, and liquid phase exfoliation. Among them, the liquid phase exfoliation method is green, convenient and efficient [4]. In this method, the interaction between the solvent and 2D MoS ₂ is assisted by ultrasound to overcome the interaction of the van der Waals force between the material bulk layers, thereby exfoliating the 2D MoS ₂ nanosheets. However, it is difficult to control the number of layers of MoS2 due to possible agglomeration of the material during the drying process [ ₅ ].

Ionic liquids (Ionic liquids, ILs) are not only used for supporting electrolytes [7], but also for electrode modification due to their low vapor pressure, high electrochemical stability, high ionic conductivity and high stability [6]. In recent years, IL has been used as an alternative to toxic liquids for large-scale synthesis of 2D materials by grinding [8,9]. The aromaticity of IL can effectively break the van der Waals force [10-12] to obtain delayered MoS ₂ . However, the reproducibility of the ion intercalation stripping method is poor, and the prepared nanosheets have a large size [7]. Therefore, efficient, high _- quality, and facile preparation of MoS2 nanosheets remains a challenge.

Graphene oxide (GO) has been widely used in electrochemical sensing applications due to its remarkable electrochemical properties. Compared with graphite or graphene, MoS2 has a lower electronic conductivity [ ₁₃ ], so hybrid materials of _MoS2 and GO may overcome this deficiency. Furthermore, MoS ₂ and GO hybrid materials may lead to improved structural compatibility and electrochemical properties due to the similar morphology and layered structure of both MoS ₂ and GO [14].

Chloramphenicol (CAP) is a broad-spectrum antimicrobial agent used to treat infectious diseases in animals[15-17], but excessive intake of CAP from food or drugs may cause severe toxic side effects[18-20]. Currently, techniques for detecting CAP mainly include high performance liquid chromatography [21], reversed-phase injection chromatography [22], gas chromatography-mass spectrometry [23], liquid chromatography-mass spectrometry [24], etc. These traditional analytical methods require expensive equipment and complicated experimental procedures, while electrochemical methods have attracted more and more attention because of their simplicity, low cost, and high sensitivity. Most of the related nanomaterials synthesis methods reported so far are complex or involve toxic substances [25-27], thus green and sensitive preparation of electrochemical sensors still needs to be explored.

Contents of the invention

(1) Technical problems to be solved

_The number of layers of MoS2 is difficult to control due to possible agglomeration of the material during the drying process. The reproducibility of the ion intercalation and exfoliation method is poor, and the prepared nanosheets are large in size. Therefore, the efficient, high _- quality and simple preparation of MoS2 nanosheets is still an urgent problem in this field. In addition, green and sensitive electrochemical sensors still need to be explored and solved in this field.

(2) Technical solution

In order to solve the above problems, the present invention provides the following technical solutions:

In one aspect, the present invention provides a composite material based on ionic liquid molybdenum disulfide and graphene oxide, characterized in that: the composite material has the formula MoS ₂ -IL/GO.

In one embodiment, the IL is 1-butyl- ₃ -methylimidazolium tetrafluoroborate [BMIM]BF4. However, any suitable IL can be used in the present invention, and the present invention is not limited to 1-butyl-3-methylimidazolium tetrafluoroborate.

In another aspect, the present invention provides a method for preparing the aforementioned composite material of molybdenum disulfide and graphene oxide based on ionic liquid, wherein the method comprises the steps of:

(1) Move MoS ₂ and IL into DMF and sonicate for 15 hours;

(2) Add the substance of step (1) to GO, and sonicate the mixture for another 30 minutes at room temperature;

(3) Centrifuge, wash the black matter with water and redisperse in DMF to obtain MoS ₂ -IL/GO nanocomposite.

Preferably, the IL is 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM]BF ₄ .

In another aspect, the present invention provides a modified electrode, which is characterized in that: the modified electrode is modified with the aforementioned composite material of molybdenum disulfide and graphene oxide based on ionic liquid.

In one embodiment, the modified electrode is a modified glassy carbon electrode. However, any suitable electrode can be used in the present invention, and the present invention is not limited to glassy carbon electrodes.

In yet another aspect, the present invention provides an electrochemical sensor, which is characterized in that: the electrochemical sensor includes the aforementioned glassy carbon electrode.

In yet another aspect, the present invention provides the application of the aforementioned electrochemical sensor in the detection of chloramphenicol.

Preferably, the detection limit of the detection is 0.047 μmol·L ^-1 .

In some embodiments, the application is for the determination of chloramphenicol in eye drops, milk and urine samples.

(3) Effective effect

The inventors of the present application synthesized a new composite material based on ionic liquid-assisted delayered molybdenum disulfide and graphene oxide through a green and efficient method, and used it to develop a high-sensitivity electrochemical sensor for the determination of chloramphenicol CAP (CAP), achieved significant technical effects, as follows:

(1) The preparation method is simple and efficient; the morphology and structure of the synthesized materials were characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction, and the results confirmed the synthesis of MoS ₂ -IL/GO.

(2) Electrochemical characterization was performed by cyclic voltammetry and electrochemical impedance spectroscopy, and the glassy carbon electrode (GCE) modified by the new MoS ₂ -IL/GO composite material prepared by the present invention showed excellent Electrochemical performance and electrocatalytic ability.

(3) Under optimum conditions, the electrochemical sensor of the present invention can realize the highly sensitive measurement to CAP, has wide detection range, low detection limit, good reproducibility, good stability, and shows good performance when detecting actual samples. electrochemical performance. Under the optimized conditions, the sensor showed linear response to the current at 0.1-400 μmol L ^-1 CAP concentration with a detection limit of 0.047 μmol L ^-1 and was successfully used in eye drops, milk and urine samples Determination of CAP.

Description of drawings

The present invention will be described in detail in conjunction with the drawings and specific embodiments, and the implementation scope of the present invention is not limited thereto.

Fig. 1 is the SEM image of MoS ₂ (A), MoS ₂ -IL (B), GO (C) and MoS ₂ -IL/GO (D, E), and the TEM image of MoS ₂ -IL/GO (F).

Fig. 2 is the Raman spectrogram (A) and XRD pattern (B) of MoS ₂ , MoS ₂ -IL and MoS ₂ -IL/GO.

Figure 3 is the CV diagram (A) of the modified electrode in PBS (pH 7) with 200μmol·L ^-1 CAP, and the scan rate is 100mV·s ^-1 ; the modified electrode is in 5mmol·L ^-1 Fe(CN) ₆ EIS pattern of ^3-/4- 0.1mol·L ^-1 KCl (B). Bare GCE (a), MoS ₂ /GCE (b), MoS ₂ -IL/GCE (c), GO/GCE (d) and MoS ₂ -IL/GO/GCE (e).

Figure 4 is the DPV curves of 200 μmol L ^-1 CAP detected on MoS ₂ -IL/GO/GCE with different modified volumes (A) and pH (C); the relationship between peak current intensity and modified volume (B), pH and peak Linear relationship of potential (D).

Figure 5 (A) is the CV curve (a) of MoS ₂ -IL/GO/GCE in 200 μmol·L ^-1 CAP in 0.1mol·L ^-1 PBS (pH 7); graph (B) is the peak current vs. Linear relationship between scan rates.

Figure 6 shows the DPV curves of 0.1-400μmol·L ^-1 CAP (A) and 0.1-10μmol·L ^-1 CAP (B) on MoS ₂ -IL/GO/GCE, and the relationship between the peak current intensity and the CAP concentration Calibration curve. am: 0.1, 0.5, 1, 3, 7, 10, 20, 40, 60, 80, 100, 150, 200, 300, 400 μmol·L ⁻¹ CAP.

Detailed ways

The present invention will be further described below in conjunction with specific examples. The raw materials and equipment used in the examples are well known to those skilled in the art, and all of them can be purchased or easily obtained or prepared in the market.

One, preparation embodiment

1. Reagents and Instruments

GO (>99%, Nanjing Jicang Nano Technology Co., Ltd.); MoS ₂ (99%, Sigma-Aldrich), [BMIM]BF ₄ (97%, Shanghai Macklin Biochemical Technology Co., Ltd.); N,N-Dimethicone Dimethyl formamide (DMF, >99.5%, Shanghai Macklin Biochemical Technology Co., Ltd.) and CAP (≥98%, Beijing Huamaike Biotechnology Co., Ltd.). All chemical reagents used were of analytical grade.

S-4800 (Hitachi, Japan) scanning electron microscope (Scanning electron microscope, SEM) and JEM-2100F (Electronics Corporation, Japan) transmission electron microscope (Transmission electron microscope, TEM) were used for surface morphology studies. X-ray diffraction (X-ray diffraction, XRD) was measured on D/max-2600PC (Rigaku, Japan), and Raman spectrum was measured on Invia-reflex (Renishaw, UK). CHI760E electrochemical workstation (Shanghai Chenhua Instrument Co., Ltd., China), a conventional three-electrode system consisting of Ag/AgCl (saturated KCl) as the reference electrode, platinum column as the auxiliary electrode, and modified GCE as the working electrode.

2. Preparation of MoS ₂ -IL/GO nanocomposites

MoS ₂ -IL composites were prepared by ultrasonic exfoliation. 40 mg MoS ₂ and 200 μL IL([BMIM]BF ₄ ) were transferred to 40 mL DMF and sonicated for 15 hours. Then 1 mL of MoS ₂ -IL (1 g L ^-1 ) was added to 1 mL of GO (1 g L ^-1 ), and the mixture was sonicated for another 30 min at room temperature. After centrifugation, the black matter was washed with water and dispersed in DMF again to obtain MoS ₂ -IL/GO nanocomposites. _MoS2 was prepared in the same manner without adding IL as a control.

3. Preparation of Modified GCE

The GCE surface was polished with 0.2–0.5 μm alumina powder, and then washed with ethanol and water. 3 μL of MoS2 _- IL/GO composite was dropped on the pre-cleaned GCE and dried at room temperature to prepare the modified electrode. MoS2, MoS2 _- IL and GO-modified GCE were prepared in a similar manner as controls.

2. Effect example

1. Characterization of MoS ₂ -IL/GO

As shown in Figure 1, SEM images of MoS ₂ (Figure 1A), MoS ₂ -IL (Figure 1B), GO (Figure 1C) and MoS ₂ -IL/GO (Figure 1D, Figure 1E) show the surface topographic features . Figure 1D and Figure 1E show that the MoS2 flakes are uniformly dispersed _on the surface of the GO sheet. As shown in Fig. 1F, the TEM image of MoS2 _- IL/GO shows that several _MoS2 flakes are stacked together and interconnected with GO flakes. _The results show that MoS2 and GO are well mixed, which effectively increases the surface area of the synthesized material.

As shown in Figure 2, Figure 2A depicts the Raman spectrum of the synthesized material. MoS ₂ shows major Raman active peaks at 375.8 cm ⁻¹ and 402.9 cm ⁻¹ , corresponding to E ¹ _2g and A _1g of MoS ₂ crystals, respectively. Compared with MoS ₂ , the intensities of the typical E ¹ _2g and A _1g peaks of MoS ₂ -IL and MoS ₂ -IL/GO are greatly reduced due to the delaminated structure of MoS ₂ and its dispersion on the GO surface [28]. In addition, the E ¹ _2g and A _1g peak positions of MoS ₂ -IL and MoS ₂ -IL/GO shifted, and the position of the A _1g peak of MoS2-IL moved to 401.3cm ^-1 . The results show that IL can effectively break the van der Waals force between MoS ₂ flakes, thus obtaining delayered MoS ₂ . The Raman spectra of MoS ₂ -IL/GO show the _D and _G bands of GO at 1353.2 cm ^-1 and 1585.3 cm ^-1 (ID/IG = 0.88), respectively, which are attributed to local defects/disorder and sp ² graphitized structure.

To further characterize the as-prepared materials, Fig. 2B shows the XRD patterns of MoS ₂ , MoS ₂ -IL and MoS ₂ -IL/GO. It can be observed that the main peak of _MoS appears at 14.3°, reflecting the (002) plane, and no characteristic peaks of other impurities are observed in the MoS _nanoflakes . The peak position of MoS ₂ is basically the same as that of MoS ₂ -IL, but the peak intensity of MoS ₂ -IL is significantly reduced, which is due to the fact that IL is filled into the interlayer of MoS ₂ sheets, making the material more disordered. In addition, the main diffraction peaks of GO (marked by *) were observed in the XRD pattern of MoS2 _- IL/GO, which is consistent with the results of Raman spectroscopy.

2. Electrochemical performance of the modified electrode

The electrochemical performance of the modified electrode was studied by cyclic voltammetry (Cyclic voltammetry, CV). Figure 3A shows the CV curve of the modified electrode in phosphate buffer saline (Phosphate buffer saline, PBS, pH 7) containing 200 μmol·L ^-1 CAP. Although clear redox peaks were observed on all modified electrodes, the current intensity of MoS ₂ -IL/GO/GCE was significantly larger than that of MoS ₂ /GCE, MoS ₂ -IL/GCE and GO/GCE. Compared with bare GCE, the introduction of IL improves the current response, which may be attributed to the electrochemical performance of the delayered MoS2 sheet _- modified electrode, and the synergistic catalytic effect of MoS2 and IL _on CAP [34]. The highest current intensity was observed on MoS2 _- IL/GO/GCE, which may be attributed to the further increased surface area and higher conductivity of the modified electrode due to GO. The voltammogram of MoS ₂ -IL/GO/GCE provided cathodic peaks at 0.129 V and 0.656 V in the forward scan and anodic peaks at 0.067 V in the reverse scan. The cathodic peak is explained by the irreversible reduction of the nitro group in CAP (Scheme 2, reaction a), and the anodic peak is attributed to the reversible redox reaction of the intermediate hydroxylamine group to generate the nitroso derivative [29,30], as follows Formula (reaction b, c) shown. Based on the higher peak current of the cathode peak (0.656 V), it was chosen to develop a sensitive CAP sensor.

In addition, Electrochemical impedance spectroscopy (EIS) as shown in Fig. 3B has been represented as a Nyquist plot to examine the electrical properties of the modified electrode. Fe(CN) ₆ ^3-/4- as a redox probe. The diameter of the semicircle in the Nyquist diagram corresponds to the charge transfer resistance (Charge transfer resistance, R _ct ), and the diameter of the semicircle of the EIS curve of different modified electrodes is different. The order of R _ct intensity is: MoS ₂ -IL/GO/GCE<GO/GCE<MoS ₂ -IL/GCE<MoS ₂ /GCE<GCE. The results show that all the modified electrode materials can reduce the electrode R _ct . Among them, due to the higher conductivity of the synthesized material, the Rct of MoS ₂ -IL/GO/GCE is significantly lower than that of bare GCE and the control electrode. Both CV and EIS results show that the MoS ₂ -IL/GO modified electrode has good electrochemical performance.

3. Optimization of experimental conditions

To achieve sensitive detection of CAP, the conditions of modification amount and pH were systematically optimized. As shown in Figure 4A, the current intensity was the highest when 3 μL of MoS ₂ -IL/GO suspension (1.0 mg mL ^- 1 ) was dropped onto the GCE surface, and the current intensity decreased with further increase in the volume of the modifier (Figure 4B). This is because MoS ₂ -IL/GO can effectively increase the surface area of the electrode, but the stacking of thicker layers may hinder the conductivity of the electrode. Choose the optimal volume of MoS ₂ -IL/GO suspension as 3 μL.

Figure 4C shows the effect of PBS buffer pH. The CAP peak current increased with increasing pH from 5 to 7 and reached a maximum at pH 7. From pH 7 to pH 9, the peak current decreases gradually. In addition, there was a good linear relationship between different pH values and peak potentials (Fig. 4D), which indicated that protons were involved in the process of redox reactions [36]. Therefore, a PBS solution with an optimum pH of 7 was selected.

In addition, to further determine the reaction mechanism between MoS ₂ -IL/GO/GCE and CAP, the effect of scan rate on the redox peak current was explored (Fig. 5A). When the scan rate was 20mV s ^-1 -140mV s ^-1 , the redox current increased with the increase of the scan rate, and there was a linear relationship between the peak current and the scan rate (Fig. 5B), which is when detecting CAP Electrode surfaces are constrained by the characteristic behavior of electrocatalytic processes.

4. Detection of different concentrations of CAP

Different concentrations of CAP were detected by DPV under optimal conditions. As shown in Figure 6A and Figure 6B, as the CAP concentration increased, the reduction peak current at 0.604 V also gradually increased, and was proportional to the CAP concentration in the range of 0.1–400 μmol L ⁻¹ . The regression equations are I(μA)=0.3018C _CAP -1.331(0.1-400μmol·L ^-1 , R ² =0.9941) and I(μA)=0.3665C _CAP +0.0379(0.1-10μmol·L ^-1 , R ² = 0.9967). The detection limit of CAP was 0.047 μmol·L ^-1 (S/N=3). By comparing with the previously reported electrochemical sensors for CAP detection (Table 1), this sensor showed comparable or even better performance.

Table 1. Comparison between different electrochemical sensors for detecting CAP.

^a RGO (Reduced graphene oxide) is reduced graphene oxide, and AuNPs (Au nanoparticles) are gold nanoparticles.

5. Stability, repeatability and reproducibility

After the modified electrode was stored at room temperature for 10 days and used to detect 200 μmol·L ^-1 CAP, its analytical performance remained 92.94% of that of the original electrode, indicating that the sensor had good stability. Ten repeated measurements of 200 μmol L ^-1 CAP were performed on a single modified electrode, and the electrode showed excellent repeatability with a relative standard deviation (RSD) of 2.605%. In addition, by using 10 modified electrodes to measure 200 μmol L ^-1 CAP, the RSD was 2.877%, indicating that the modified electrodes had good reproducibility.

6. Actual sample analysis

The application potential of MoS ₂ -IL/GO/GCE to detect CAP was evaluated by testing different types of real samples, such as CAP eye drops, milk and urine. CAP eye drops, milk and urine were diluted 40, 5 and 5 times with 0.1mol·L ^-1 PBS (pH 7) solution respectively. The results are shown in Table 2. The recoveries of CAP in actual samples were 90.70%-100.4%. The results show that MoS ₂ -IL/GO/GCE is a promising electrochemical sensor when applied to real sample analysis.

Table 2. Spiked recovery of MoS ₂ -IL/GO/GCE in real samples.

^a CAP was not detected in milk and urine.

7. Conclusion

A novel MoS2 _- IL/GO composite was successfully synthesized through a facile, green and efficient method. SEM, TEM, Raman spectroscopy and XRD results confirmed the synthesis of MoS ₂ -IL/GO. The MoS2-IL/GO modified GCE exhibits excellent electrochemical performance and electrocatalytic ability. Under optimal conditions, the electrochemical sensor can achieve high-sensitivity determination of CAP with wide detection range, low detection limit, good reproducibility, good stability, and exhibits good electrochemical performance when detecting real samples.

So far, those skilled in the art should appreciate that, although a number of exemplary embodiments of the present invention have been shown and described in detail herein, without departing from the spirit and scope of the present invention, the disclosed embodiments of the present invention can still be used. Many other variations or modifications consistent with the principles of the invention are directly identified or derived from the content. Accordingly, the scope of the present invention should be understood and deemed to cover all such other variations or modifications.

References of the present invention are as follows:

1. Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, Grigorieva IV, Firsov AA(2004) Electric field effect in atomically thin carbonfilms. Science 306(5696):666-669

2. Kong RM, Ding L, Wang Z, You J, Qu F (2015) Anovel aptamer-functionalized MoS 2nanosheet fluorescent biosensor for sensitive detection of prostate specific antigen. Anal Bioanal Chem 407(2):369-377

3. Radisavljevic B, Radenovic A, Brivio J, Giacometti V, Kis A (2011) Single-layer MoS2transistors. Nat Nanotechnology 6(3):147-150

4. Yuk JM, Park J, Ercius P, Kim K, Hellebusch DJ, Crommie MF, Lee JY, ZettlA, Alivisatos AP (2012) High-resolution EM of collagen nanocrystal growth using graphene liquid cells. Science 336(6077):61- 64

5.Guan G, Zhang S, Liu S, Cai Y, Low M, Teng CP, Phang IY, Cheng Y, Duei KL, Srinivasan BM (2015) Protein Induces Layer-by-Layer Exfoliation of TransitionMetal Dichalcogenides.J Am Chem Soc 137(19):6152-6155

6. Kim J, Kim S(2014) Preparation and electrochemical property of ionicliquid-attached graphene nanosheets for an application of supercapacitor electrode. Electrochim Acta 119(6):11-15

7. Abbasi P, Asadi M, Liu C, Sharifi-Asl S, Sayahpour B, Behranginia A, Zapol P, Shahbazian-Yassar R, Curtiss LA, Salehi-Khojin A (2017) Tailoring the Edge Structure of Molybdenum Disulfide toward Electrocatalytic Reduction of Carbon Dioxide.ACS Nano 11(1):453-460

8. Zhang W, Wang Y, Zhang D, Yu S, Zhu W, Wang J, Zheng F, Wang S, Wang J (2015) A one-step approach to the large-scale synthesis of functionalized MoS2nanosheets by ionic liquid assisted grinding .Nanoscale 7(22):10210-10217

9.Shang NG, Papakonstantinou P, Sharma S, Lubarsky G, Li M, Mcneill DW, Quinn AJ, Zhou W, Blackley R(2012) Controllable selective exfoliation of high-quality graphene nanosheets and nanodots by ionic liquid assistedgrinding.Chem Commun 48 (13):1877-1879

10. Wang Y, Ou JZ, Balendhran S, Chrimes AF, Mortazavi M, Yao DD, Field MR, Latham K, Bansal V, Friend JR(2013) Electrochemical Control of Photoluminescence in Two-Dimensional MoS2 Nanoflakes.Acs Nano 7(11) :10083-10093

11. Asadi M, Kumar B, Liu C, Phillips P, Yasaei P, Behranginia A, Zapol P, Klie RF, Curtiss LA, Salehi-Khojin A (2016) Cathode Based on Molybdenum DisulfideNanoflakes for Lithium-Oxygen Batteries.ACS Nano 10 (2): 2167-2175

12. Lau VW, Masters AF, Bond AM, Maschmeyer T (2012) Ionic-liquid-mediated active-site control of MoS2 for the electrocatalytic hydrogen evolution reaction. Chem-Eur J 18(26):8230-8239

13.Wang GX, Bao WJ, Wang J, Lu QQ, Xia XH(2013) Immobilization and catalytic activity of horseradish peroxidase on molybdenum disulfidenosheets modified electrode. Electrochem Commun 35(10):146-148

14. Chekin F, Teodorescu F, Coffinier Y, Pan GH, Barras A, Boukherroub R, Szunerits S (2016) MoS2/reduced graphene oxide as active hybrid material for the electrochemical detection of folic acid in human serum. Biosens Bioelectron 85:807-813

15. Armenta S, Guardia MDL, Abad-Fuentes A, Abad-Somovilla A, Esteve-Turrillas FA (2016) Highly selective solid-phase extraction sorbents for chloramphenicol determination in food and urine by ion mobility spectrometry. Anal Bioanal Chem 408 (29): 1-9

16.Kong FY,Chen TT,Wang JY,Fang HL,Fan DH,Wang W(2016)UV-assistedsynthesis of tetrapods-like titanium nitride-reduced graphene oxidenanohybrids for electrochemical determination of chloramphenicol.Sensors&Actuators B Chemical 225:298-30

17. Codognoto L, Winter E, Doretto KM, Monteiro GB, Rath S (2010) Electroanalytical performance of self-assembled monolayer gold electrode for chloramphenicol determination. Microchim Acta 169(3-4):345-351

18. Wiest DB, Cochran JB, Tecklenburg FW (2012) Chloramphenicol toxicity revisited: a 12-year-old patient with a brain abscess. Journal of Pediatric Pharmacology & Therapeutics Jppt the Official Journal of Ppag 17(2):182-188

19. Duan N, Wu S, Dai S, Gu H, Hao L, Ye H, Wang Z (2016) Advances inaptasensors for the detection of food contaminants. Analyst 141(13):3942-3961

20. Bagheri Hashkavayi A, Bakhsh Raoof J, Ojani R, Hamidi Asl E (2015) Label-Free Electrochemical Aptasensor for Determination of Chloramphenicol Based on Gold Nanocubes-Modified Screen-Printed Gold Electrode. Electroanal 27(6):1449-1456

21. Satínsky D, Chocholous P, Salabová M, Solich P (2015) Simple determination of betamethasone and chloramphenicol in a pharmaceutical preparation using a short monolithic column coupled to a sequential injection system. J Sep Sci 29(16):2494-2499

22. Yadav SK, Agrawal B, Chandra P, Goyal RN (2014) In vitrochloramphenicol detection in a Haemophilus influenza model using an aptamer-polymer based electrochemical biosensor. Biosens Bioelectron 55(4):337-342

23. Yan Z, Gan N, Wang D, Cao Y, Chen M, Li T, Chen Y (2015) A"signal-on"aptasensor for simultaneous detection of chloramphenicol and polychlorinatedbiphenyls using multi-metal ions encoded nanospherical brushes astracers.Biosens Bioelectron 74(49):718-724

24. Govindasamy M, Chen SM, Mani V, Devasenathipathy R, Umamaheswari R, Joseph Santhanaraj K, Sathiyan A (2017) Molybdenum disulfide nanosheets coatedmultiwalled carbon nanotubes composite for highly sensitive determination of chloramphenicol in food sneyamples mi interfsci 485:129–136

25. Abnous K, Danesh NM, Ramezani M, Emrani AS, Taghdisi SM (2016) A novel colorimetric sandwich aptasensor based on an indirect competitive enzyme-freemethod for ultrasensitive detection of chloramphenicol. Biosens Bioelectron78:80-86

26. Karthik R, Govindasamy M, Chen SM, Mani V, Lou BS, Devasenapathy R, Hou YS, Elangovan A (2016) Green synthesized gold nanoparticles decorated graphene oxide for sensitive determination of chloramphenicol in milk, powdered milk, honey and eye drops. J colloid interf sci 475:46-56

27. Tai SY, Liu CJ, Chou SW, Chien SS, Lin JY, Lin TW (2012) Few-layer MoS2nanosheets coated onto multi-walled carbon nanotubes as a low-cost and highly electrocatalytic counter electrode for dye-sensitized solar cells.J MaterChem 22(47):24753-24759

28. Asadi M, Kumar B, Liu C, Phillips P, Yasaei P, Behranginia A, Zapol P, Klie RF, Curtiss LA, Salehikhojin A (2016) Cathode Based on Molybdenum DisulfideNanoflakes for Lithium–Oxygen Batteries.Acs Nano 10(2 ):2167

29. Yang G, Zhao F(2015) Electrochemical sensor for chloramphenicol based on novel multiwalled carbon nanotubes@molecularly imprintedpolymer.Biosens Bioelectron 64:416-422

30. Fedorczyk A, Ratajczak J, Kuzmych O, Skompska M (2015) Kinetic studies of catalytic reduction of 4-nitrophenol with NaBH 4 by means of Aunanoparticles dispersed in a conducting polymer matrix. J Solid State Electrochem 19(9): 5849-28

31. Zhang X, Zhang YC, Zhang JW (2016) A highly selective electrochemical sensor for chloramphenicol based on three-dimensional reduced graphene oxide architectures. Talanta 161:567

32. Tao Y, Huaiyin C, Tong G, Jin W, Weihua L, Kui J (2015) Highly sensitive determination of chloramphenicol based on thin-layered MoS2/polyanilinenanocomposite. Talanta 144:1324-1328

33. Borowiec J, Wang R, Zhu L, Zhang J (2013) Synthesis of nitrogen-dopedgraphene nanosheets decorated with gold nanoparticles as an improved sensor for electrochemical determination of chloramphenicol. Electrochim Acta 99:138-144.

Claims (10)

1. a kind of composite material of molybdenum disulfide and graphene oxide based on ionic liquid, it is characterised in that：The composite wood Material has formula MoS₂-IL/GO。

2. the composite material of the molybdenum disulfide and graphene oxide according to claim 1 based on ionic liquid, feature It is：The IL is 1- butyl -3- methyl imidazolium tetrafluoroborate [BMIM] BF₄。

3. a kind of composite material for preparing the molybdenum disulfide based on ionic liquid and graphene oxide of any of claims 1 or 2 Method, which is characterized in that described method includes following steps：

(1) by MoS₂It is moved in DMF with IL, ultrasound 15 hours；

(2) step (1) is added into GO obtains MoS₂-IL(1g·L^-1), and mixture is 30 minutes ultrasonic again at room temperature；

(3) it is centrifuged, black object is washed with water and is dispersed again in DMF, obtain MoS₂- IL/GO nanocomposite.

4. according to the method described in claim 3, it is characterized in that：The IL is 1- butyl -3- methyl imidazolium tetrafluoroborate [BMIM]BF₄。

5. a kind of modified electrode, it is characterised in that：The modified electrode is with of any of claims 1 or 2 based on ionic liquid The composite material of molybdenum disulfide and graphene oxide is modified.

6. modified electrode according to claim 6, it is characterised in that：The modified electrode is modified glass-carbon electrode.

7. a kind of electrochemical sensor, it is characterised in that：The electrochemical sensor includes glass carbon described in claim 5 or 6 Electrode.

8. application of the electrochemical sensor according to claim 7 in detection chloramphenicol.

9. application according to claim 8, it is characterised in that：The detection of the detection is limited to 0.047 μm of olL^-1。

10. application according to claim 8, it is characterised in that：The application is for eye drops, milk and urine sample The measurement of middle chloramphenicol.