Preparation,Properties And Sensing Applications Of Rare Earth Organic Framework Nanostructures

In recent years,metal organic frameworks（MOFs）have been developed and successfully applied in different fields.In particular,rare earth elements as metal ions with organic ligands combine to form lanthanide metal-organic framework materials,which have both the luminescence properties of RE and the frame structure of MOFs,as well as their low toxicity and good biocompatibility.Up to now,the synthesis methods of Ln-MOFs materials have been nearly mature,but the application of Ln-MOFs materials in the fields of electrochemiluminescence（ECL）and fluorescence（FL）was stillin thedevelopment stage.Thispaper applied thevarious RE and the same organic ligand material,4,4’,4’-（（1,3,5-triazine-2,4,6-trityl）tris（azanediyl））tribenzoic acid,based on the different preparation methods to synthesis the rodlike nanomaterial of Eu-TATAB,nanostructured materials with double luminescent properties of Eu/Tb-TATAB and the novel nanomaterial of Eu-TATAB-ED.The properties of these three materials were studied,and was successful to build the sensor of ECL,FL and Ultraviolet-visible（UV-vis）sensing systems,The specific research contentwas as follows:Chapter 1:In this chapter,the properties,synthesis,and applications of Ln-MOFs nanomaterials were briefly summarized,and the application of Ln-MOFs nanomaterials to the research content ofthis paperwas summarized.Chapter 2:Ulinastatin（UTI）was extracted from fresh human urine,could inhibit the activity of a variety of proteolytic enzymes,and has a certain inhibitory effect on tumor cells.In this chapter,Eu-TATAB nanomaterial was synthesized in one step by the hydrothermal reaction to explore its morphological characteristics and further explore its ECL performance.Noticeably,the ECL intensity exhibited a desirable linear relationship with the logarithm of the UTI concentration from10^-1to10⁵ng m L^-1.The linear regression equation wasΔI=1700.43 lgc _UTI+6214.35,R²=0.9955,and the detection limit were calculated to be 9.7 pg m L^-1.Additionally,the biosensor of ECL was successfullyapplied to detect UTIin theactual sample of serum.Chapter3:2,6-pyridine dicarboxylic acid（DPA）was a biomarker of Bacillus anthracis spores,which not only caused acute zoonotic infectious diseases but also was a deadly biological warfare agent.This paper introduced the preparation of dual self-luminescent MOF materials of Eu/Tb-TATABby the electrodepositionsynthesis method.The Eu/Tb-TATAB material was used in fields of ECL and FL to detect the DPA.In the field of the sensor of ECL,a linear correlation between ECL intensity and DPAconcentrations was observed over the range of 10^-9-10^-2M.The fitted linear data could be expressed asΔI=885.95 lgc _DPA+13733（R²=0.9926）,LOD=9.4×10^-10M.In the field of a sensor of FL,which was used to quantitatively detect DPAby monitoring the ratio value I₅₄₅/I₆₁₇of the characteristic peaks intensity of Tb³⁺and Eu³⁺at 545 nm and 617 nm,respectively,and the variation of DPA concentration range.The linear equation was well in the concentration range of 7×10^-5-8×10^-4M:I₅₄₅/I₆₁₇=0.3846C+0.2250,R²=0.9923,LOD=6.8×10^-6M.The sensor of ECL and the sensor system of FL successfully detected DPA in the water and serum,and possessed satisfactory results,to provide a novel measure to detect DPA in theenvironment.Chapter 4:The concentration of ethanol（C₂H₅OH）was an important index of C₂H₅OH content in alcoholic beverages.In this chapter,Eu-TATAB-ED nanomaterials were synthesized for the preparation of ECL sensor,FL and UV-vis sensing systems to detect C₂H₅OH.Follow-up experiments were conducted on the basis of response signal quenching.The three sensing platform have been successfully applied to the detection of C₂H₅OH concentration in alcoholic beverages,and the recovery rate of ECL was 99.78%～103.8%,RSD≤1.9%.The recoveries of FL were97.54%～101.7%,RSD≤3.0%.UV-vis recoveries range from 98.23%to 99.06%,RSD≤2.0%.The results show that the ECL sensor and FL and UV-vis sensor system can detect the concentrationof C₂H₅OHwell.