Preparation Of Solid State Electrochemiluminescence Sensors Based On Carbon Nanomaterials And Their Application In The Detection Of Cardiovascular Drugs

Electrochemiluminescence（ECL）is the combination of electrochemistry and chemiluminescence technology,with simple equipment,easy to operate,fast analysis,high sensitivity,wide linear range,and no external light source.During the past several decades,solid-state electrochemluminescence sensors built by modified electrodes has received considerable attention because of miniaturization and low cost,has been widely applied in many fields,such as immunoassay,environmental analysis and food analysis,drug analysis and biology analysis and so on.Due to the large specific surface area,good conductivity and size effect of carbon nanomaterials,they were widely used as modified materials in solid-state electrochemical luminescence sensor to improve the electron conduction rate.Embedding or modifying the luminescent reagent Ru（bpy）₃²⁺on the modified electrode by the composite film not only simplifies the experimental setup,but also reduces the consumption of expensive reagents.The purpose of this paper is to study the preparation of solid-state electrochemiluminescence sensors and their application in the detection of cardiovascular drugs.On the other hand,the combination of capillary electrophoresis with the sensor improves the selectivity of solid-state electrochemiluminescence sensor.The main research contents and research results are as follows:1.In this study,the reduced graphene oxide（rGO）and silver nano particles（AgNPs）were synthesized by hydrothermal method.The rGO-AgNPs show the good conductivity and large specific surface.We prepared a regenerable solid state ECL sensor based on rGO-AgNPs-Nafion loading Ru（bpy）₃²⁺.The prepared ECL sensor was used for the determination of metoprolol in mice plasma.The experimental results show that under the optimum conditions,the proposed ECL sensor exhibited excellent performances with a linear range from 1×10^-11 to 1×10^-5 mol/L,and the detection limit of 3.3×10^-12 mol/L（S/N=3）for metoprolol.The recoveries were from 94.0%to 98.3%.RSDs were from 3.0%to 3.2%.2.The rGO-ZnO composite was synthesized by one-pot hydrothermal method,and then mixed with Nafion and luminescent reagents.The ECL sensor based on rGO-ZnO-Nafion-Ru（bpy）₃²⁺ was constructed to determine the trimetazidine（TMZ）hydrochloride in human plasma.Under the optimized conditions,the ECL sensor in the concentration range of trimetazidine hydrochloride from 5×10^-9 to 1×10^-4 mol/L showed a good linear relationship.The linear equation was IECL=842.1 Log(CTMZ/mol.L^-1)+7685（r²=0.9950）with a detection limit of 1.6×10^-9 mol/L（S/N=3）.Comparing with the use of bare platinum electrode as working electrode,the ECL sensor can significantly improve the detection sensitivity of TMZ.The recoveries were from 98.3%to 97.8%.RSDs ware less than 3.3%.3.Graphene quantum dots（GQD）was synthesized by carbonizing the citric acid according to hydrothermal method.Based on the enhancement of Ru（bpy）₃²⁺by GQD modified electrode to prepare an ECL sensor,it coupled with the capillary electrophoresis for the determination of Salafloxacin in milk.The CE-ECL sensor parameters that affect separation and detection were optimized.Under the optimal conditions,the linear range was between 0.0005 and 5μg/mL for salafloxacin,and the detection limit was 0.16ng/mL.Therecoveries were from 91.5 to 97,1%.The thesis consists of four chapters.Chapter 1 is the introduction,Chapter 2 for an solid state electrochemiluminescence sensor based on rGO-AgNPs composites and the detection of metoprolol,Chapter 3 for an solid state electrochemiluminescence sensor based on rGO-ZnO composite and its application to determination of trimetazidine hydrochloride,chapter 4 for the constructed GQDs modified solid-state electrochemiluminescence sensor coupled with capillary electrophoresis and its application to the detection of salafloxacin in milk.Chapters 2 to 4 are my own research work.