Synthesis Of Lanthanide Metal Organic Gels Materials And Their Applications In Electrochemiluminescence Bioanalysis

Electrochemiluminescence（ECL）analysis method is favored by researchers due to its high sensitivity,low background interference,wide dynamic range,and spatiotemporal controllability of luminescence.The applications of classical luminescent systems such as ruthenium bipyridine/tri-n-propylamine(Ru（bpy）₃²⁺/TPr A)and luminol/hydrogen peroxide（Luminol/H₂O₂）systems are still limited because TPr A is toxic and volatile,Luminol has problem of poor modifiability and unstable luminescence.In recent years,the research of ECL analysis based on nanomaterials with excellent performance has been received much attention.Quantum dots,carbon dots,metal organic frameworks,metal oxides,etc.have been successively applied to construct new ECL systems.However,the above-mentioned synthesis methods of nanomaterials have disadvantages such as harsh reaction conditions（using inert atmosphere,high temperature and pressure）,and complicated reactions（requiring multi-step reactions）.Therefore,establishing a new synthesis method with mild reaction conditions and simple reaction process,and synthesizing new nanomaterials with excellent ECL properties has gradually become an important academic growth point of current ECL research.The aim of this thesis is to study the synthesis of lanthanide metal-organic gels and their application as ECL substances in bioanalysis.Chapter 1.Firstly,the basic principles of ECL and common ECL systems are introduced;Secondly,the preparation of emerging smart soft material metal-organic gels and the research progress in the field of ECL are summarized;Finally,the research content and research significance of this thesis are clarified.Chapter 2.Study on multichannel electrochemiluminescence behavior of thermosetting lanthanide metal-organic gels.For the first time,five thermosetting lanthanide metal-organic gels（La-MOGs/Ce-MOGs/Eu-MOGs/Tb-MOGs/Dy-MOGs）were synthesized under the action of three-phase solvent of N,N-dimethylformamide,methanol and water,using lanthanide ions(La³⁺/Ce³⁺/Eu³⁺/Tb³⁺/Dy³⁺)and 5,5’,5’’-（（1,3,5-triazine-2,4,6-triyl）tris（azanediyl））triisophthalic acid（H₆L）as precursors.The ECL behavior of five gels materials and the possible ECL mechanism in the presence of three different cathodic co-reactants（K₂S₂O₈,H₂O₂,or Na₂C₂O₄）were investigated,respectively.The results have shown that the synthesized five thermosetting lanthanide metal-organic gels materials exhibit different intensities and multichannel ECL responses.The ECL properties of Tb-MOGs are far superior to those of the other four gel materials.The enhancement of ECL signaling is attributed to the efficient sensitization of Tb³⁺ions by H₆L in Tb-MOGs（intrinsic factors）and the promotion of co-reactive reagents（exogenous causes）.This work provides new ideas for the synthesis of new ECL lanthanide metal-organic gels materials.Chapter 3.Self-luminescent lanthanide-based metal-organic gels as electrochemilumines-cence emitters for bioanalysis applications.In this work,we report self-luminescent lanthanide-based metal-organic gels（Ln-MOGs）as ECL emitters,which were prepared from precursors containing 5-boronoisophthalic acid（5-bop）and Tb（NO₃）₃·5H₂O.The optical,electrochemical and ECL properties of Ln-MOGs modified glassy carbon electrode in aqueous phase were investigated in detail.The Ln-MOGs showed excellent ECL performance without additional co-reactants.The as-prepared Ln-MOGs remained in an intact semi-solid gel state after being stored for 6 months and the ECL intensity did not change significantly.Based on the difference in the interaction force between Ln-MOGs and different bases A/T/C/G/U in nucleic acid chains,a new analytical method for distinguishing nucleic acids was initially established.