Synthesis of Three‑Dimensional Reduced Graphene Oxide/β‑Cyclodextrin Complex and Its Electrochemical Detection of Levofloxacin in Water

doi:10.19894/j.issn.1000-0518.210335

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (7): 1129-1137.DOI: 10.19894/j.issn.1000-0518.210335

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Synthesis of Three‑Dimensional Reduced Graphene Oxide/β‑Cyclodextrin Complex and Its Electrochemical Detection of Levofloxacin in Water

Qing-Fang NIU, Xin AI, Yi-Xuan WANG, Fang-Jiu HE, Bi LUO, Wen-Ting LIANG(), Chuan DONG()

College of Chemistry and Chemical Engineering，Institute of Environmental Science，Shanxi University，Taiyuan 030006，China

Received:2021-07-09 Accepted:2021-10-02 Published:2022-07-01 Online:2022-07-11
Contact: Wen-Ting LIANG,Chuan DONG
About author:dc@sxu.edu.cn
liangwt@sxu.edu.cn；
Supported by:
the National Natural Science Foundation of China(21976113)

Abstract

Abstract:

The β?cyclodextrin modified three-dimensional reduced graphene oxide （3D-rGO/β?CD） composites were successfully constructed. The composite was characterized by scanning electron microscopy， Fourier transform infrared spectroscopy， thermal gravimetric analysis and Raman spectroscopy， and its morphology and structure were analyzed. A novel electrochemical sensor （3D-rGO/β?CD/GCE） was constructed by grafting the composite on the surface of glassy carbon electrode （GCE）. Levofloxacin （LEV） was detected by differential pulse voltammetry （DPV） using a 3D-rGO/β-CD/GCE electrochemical sensor. Among them， the porous 3D-rGO has excellent electrical conductivity， large specific surface area， and good chemical stability， while the modified β-cyclodextrin can combine with guest molecules in its ring cavity to form supramolecular inclusion complex， which can effectively identify LEV. The results show that 3D-rGO/β-CD/GCE has a wide linear range （1~150 μmol/L） and a detection limit of 0.33 μmol/L for levofloxacin under the optimal experimental conditions. The modified electrode also shows good selectivity and stability. In addition， it is successfully applied to LEV detection in real water samples， indicating that the sensor has certain potential application.

Key words: β?Cyclodextrin, Three-dimensional reduced graphene oxide, Electrochemical detection, Levofloxacin

CLC Number:

O655

Qing-Fang NIU, Xin AI, Yi-Xuan WANG, Fang-Jiu HE, Bi LUO, Wen-Ting LIANG, Chuan DONG. Synthesis of Three‑Dimensional Reduced Graphene Oxide/β‑Cyclodextrin Complex and Its Electrochemical Detection of Levofloxacin in Water[J]. Chinese Journal of Applied Chemistry, 2022, 39(7): 1129-1137.

Figures/Tables 11

Fig.1 Illustration of the procedure for preparing 3D-rGO/β-CD， and electrochemical sensing of levofloxacin （LEV）

Fig.2 SEM images of （A） 3D-rGO and （B） 3D-rGO/β-CD

Fig.3 （A） FT-IR spectra and （B） TGA curves of β-CD， 3D-rGO and 3D-rGO/β-CD；（C） Raman spectra of 3D-rGO and 3D-rGO/β-CD

Fig.4 Nyquist curves （A） and cyclic voltammograms （B） of bare GCE （a）， 3D-rGO （b） and 3D-rGO/β-CD （c）modified GCE in 0.1 mol/L PBS （pH= 7.0） containing 5 mmol/L ［Fe（CN）6］3-/4- and 0.1 mol/L KCl； modified GCEs in 0.1 mol/L PBS （pH= 3.0） containing 200 μmol/L LEV（C）

Fig.5 （A） Influence of different sweep rates （a. 10 mV/s， b.40 mV/s， c.80 mV/s， d.120 mV/s， e.160 mV/s， f.200 mV/s） on the detection of 2 mmol/L LEV by 3D-rGO/β-CD /GCE；（B） Linear relation between the LEV oxidation peak current （Ip） and the sweep rate （v）；（C） Effect of pH on the detection of 2 mmol/L LEV by 3D-rGO/β-CD /GCE；（D） Linear relationship between the LEV oxidation peak potential （Ep） and pH

Fig.6 Effect of （A） the enrichment time and （B） modification amount on the detection of 2 mmol/L LEV by 3D-rGO/β-CD/GCE

Fig.7 （A） DPVs of determination towards different concentrations of LEV of 3D-rGO/β-CD modified GCE in 0.1 mol/L PBS（pH=7.0）；（B）The calibration curve for the determination of LEV

Table 1 Comparison of dif ferently modified electrodes for determination of LEV

修饰电极 Modified electrode	方法 Method	线性范围 Linear range/（μmol·L^-1）	检测限 LOD/（μmol·L^-1）	参考文献 Ref.
AgNPs/CeO₂?Au/GCE	DPV	0.03~10.0	0.01	［17］
PoAP/GQD/GCE	DPV	0.05~100	0.01	［18］
Co/Ni?MOF/GCE	LSV	0.1~500	0.022	［19］
PoAP/MWCNT/GCE	LSV	3.0~200	3.3	［20］
CuNPs/rGO/GCE	DPV	0.1~2.5	0.017	［21］
pABSA/GR/GCE	DPV	1~600	0.33	［22］
NiO?AgNPs/GCE	SWV	0.25~100	0.027	［23］
MIP/G?Au/GCE	DPV	1~100	0.53	［24］
3D?rGO/β?CD/GCE	DPV	1~150	0.33	This work

Fig.8 （A） DPV responses of 3D-rGO/β-CD/GCE in 0.1 mol/L PBS （pH =7.0） for 100 μmol/L LEV（a）， Ade （b）， Glu （c）， Asc（d） and the equal mixture of them. （B） Amperometric responses of the 3D-rGO/β-CD/GCE for the addition of 100 μmol/L LEV and 200 μmol/L Asc， Glu， KCl， LEV， Ade and 100 μmol/L LEV in 0.1 mol/L PBS （pH = 7.0）

Table 2 Determination of LEV in Fenhe river water with 3D?rGO/β?CD/GCE

实际样品 Sample	加入量 Added/（μmol·L^-1）	检测量 Found/（μmol·L^-1）	回收率 Recovery/%	相对标准偏差 RSD/%
1	5.00	5.21	104.2	2.12
2	10.00	10.08	100.8	1.83
3	20.00	19.81	99.05	1.16
4	50.00	49.08	98.16	1.74
5	60.00	60.15	100.25	2.98

Fig.9 The cartograms of （A） storage stability，（B） repeatability and （C） reproducibility of the 3D-rGO/β-CD/GCE sensor

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Synthesis of Three‑Dimensional Reduced Graphene Oxide/β‑Cyclodextrin Complex and Its Electrochemical Detection of Levofloxacin in Water

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