| The 21st century is a time of development and crisis,and diseases and environmental problems are the core problems that human beings face and need to solve urgently.The detection of clinically relevant biomolecules is the basis of understanding their biological and physiological functions and developing corresponding clinical diagnosis to realize the early detection,early diagnosis and early treatment of diseases.Rapid and on-site detection of environmental pollutants is very important because it is the basis for timely collection,transmission and release of pollutant information and subsequent evaluation,supervision and treatment.Though the polymer modified electrodes by electrochemical polymerization have attracted considerable attention in the immediate detection of clinically relevant biomolecules and environmental pollutants,but the sensing performance of polymer modified materials still need to be improved and enhanced unceasingly,to adapt to the requirements of the development of the new medical system and the increasing global environmental pressure for the testing science.This paper aims to realize modulation of structure and functionalization of the polymer modified electrode material based on electrochemical polymerization by adjusting electrochemical polymerization conditions,functionalization,imprinting and composite to prepare novel polymer and its composite modified electrode so as to continuously optimize the sensor selectivity and sensitivity.The specific content is as follows:In chapter 1,the development of polymer modified electrodes based on electrochemical polymerization is reviewed systematically.Firstly,the concepts of chemical sensor and chemical modified electrode and various electrode modification methods were introduced briefly.Then the types and the preparation methods of polymer modified electrode were introduced emphatically,and then the principle,characteristics,classification and various influencing factors of electrochemical polymerization were introduced in detail.The characteristics,preparation methods,existing problems,research progress and prospect of the nanomaterial-polymer composite and molecularly imprinted polymer modified electrodes were discussed.On the basis of above,our work ideas and research contents was put forward.Chapter 2,electrochemical preparation of two nanostructured poly(sulfosalicylic acid)films with different morphologies and properties for selective sensing of dopamine:comparative study.In the two solvent systems,room temperature ionic liquid and aqueous solution,two nanostructured poly(sulfosalicylic acid)films were synthesized on the surface of glassy carbon electrode via potentiodynamic electrochemical polymerization,and the polymerization mechanism was discussed.A comparative study was conducted on two.poly(sulfosalicylic acid)films synthesized in different solvents,and the effects of different solvents on the morphology and properties of the resulting poly(sulfosalicylic acid)films were evaluated,and the sensing properties of two poly(sulfosalicylic acid)film modified glassy carbon electrodes were studied using dopamine as the model analyte.The results show that the poly(sulfosalicylic acid)film prepared from aqueous solution had a better detection limit of 0.03μmol · L-1 while the reproducibility and stability of the poly(sulfosalicylic acid)film synthesized from room temperature ionic liquid were better.These two nanostructured poly(sulfosalicylic acid)films synthesized by adjusting the experimental conditions of electrochemical polymerization have modulable selective permeability,which has different detection effect on target molecule.Chapter 3,electrochemical preparation of surface molecularly imprinted poly(3-aminophenylboronic acid)/MWCNTs nanocomposite for sensitive sensing of epinephrine.A surface molecularly imprinted polymer/multi-walled carbon nanotube nanocomposite modified electrode was successfully prepared via potentiodynamic electrochemical polymerization on the surface of MWCNTs modified glassy carbon electrode with 3-aminophenylboronic acid as the monomer and epinephrine as template molecule,and the electropolymerization mechanism of 3-aminophenylboronic acid in the presence or absence of template molecules was discussed.The preparation method features of facile operation,easy and complete removal of imprinting molecule by combining chemical and electrochemical methods and uniform distribution of the imprinted sites.The sensing performance of the surface molecularly imprinted polymer composite,MWCNT and non-imprinted polymer composite modified electrodes were compared for epinephrine detection.The surface molecularly imprinted polymer composite modified electrode has better detection performance to epinephrine,with a wider linear range of 0.2-800μmol·L-1,with a lower detection limit of 35 nmol-L-1.The surface molecularly imprinted polymer composite modified electrode was used to detect epinephrine in human serum and real injection samples under the optimal sensing conditions,and the recovery and relative standard deviation are satisfactory.The experimental results showed that the sensing performance of the modified electrode was improved significantly after the polymer modified material was combined with carbon nanomaterial and imprinted on the surface of carbon nanomaterial.The surface molecularly imprinted polymer composite modified electrode has a good application prospect in the field of clinically relevant biomolecules detection.Chapter 4,electrochemical preparation of poly(3-aminophenylboronic acid-cytidine)/MWCNTs nanocomposite for sensitive sensing of silver ions.A polymer modified electrode rich in cytosine was successfully prepared via one-step potentiodynamic electrochemical polymerization on the surface of MWCNTs modified glassy carbon electrode with boronate ester between 3-aminophenylboronic acid and cytidine as the monomer and applied to selectively adsorption and in-situ reaction of silver(1)ions for electrochemical detection.The polymerization mechanism in the presence and absence of cytidine was also discussed.The sensing performance of poly(3-aminophenylboronic acid-cytidine)composite,MWCNT and poly(3-aminophenylboronic acid)composite modified electrodes were compared for silver(Ⅰ)ions detection.The poly(3-aminophenylboronic acid-cytidine)composite modified electrode has enhanced specific recognition ability and high sensitivity for silver(Ⅰ)ions detection.Under the optimal sensing conditions,the linear detection range of the poly(3-aminophenylboronic acid-cytidine)composite modified electrode for silver()ions is 0.2-60μmol·L-1,and the detection limit is 0.080μmol·L-1.The experimental results showed that the sensing performance of the polymer modified electrode was improved significantly by functionalization of polymer modified material and composite with carbon nanomaterial. |
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