Synthesis,Properties And Application Of Flavonols And Quinolones Derivatives And Their Rare-earth Complexe

Flavonols and 2-quinolinone derivatives are widely used in the field of biopharmaceutics as natural organic compounds,and most of them have good fluorescence properties,which attracted the attention of researchers in the fields of fluorescent materials and biomarkers.In addition,a variety of coordination atoms can be introduced to flavonols or 2-quinolinone precursors to form a stable complex with the rare earth elements in order to optimize the fluorescence properties and expand the application.In this thesis,four novel flavonol ligands and six novel 2-quinolinone ligands were designed and synthesized.Their structures were verified and the fluorescence properties were explored.The ligand with the best fluorescence performance was coupled to BSA and the fluorescence properties were investigated.The corresponding rare earth complexes were prepared,and the composition and fluorescence properties of the target complexes were investigated.(1)The 4'-flavonol derivatives(A)was prepared from 2-hydroxyacetophenone and 4-benzaldehyde derivatives;A react with methyl 4-(2-chloroacetamido)benzoate(B)yield the final product 2-phenyl-3-oxo-acetylbenzoate derivatives(H1?4).All of the four novel ligands showed strong cyan fluorescence.The fluorescence performs the best in the polar proton solvents,and the fluorescence emission peaks were red-shifted with the polarity increase.The optimal concentration of the four ligands was 500 ?M,H4(R=-C1)has the best fluorescence performance under optimal solvent and concentration,and the fluorescence quantum yield is 0.237.The ligand H1?4 were coordinated with rare earth(Eu3+,Tb3+)to obtain the corresponding rare earth complexes.The general formula can be denoted as ReH1?4(NO3)3·H2O(Re=Eu3+,Tb3+).The target Eu3+and Tb3+complexes showed the characteristic light respectively,and the fluorescence performance was affected by the substituent groups in the ligands as ReH4(NO3)3·H2O(R=-C1)>ReH3(NO3)3·H2O(R=-OCH3)>ReH2(NO3)3·H20(R=-CH3)>ReH1(NO3)3·H2O(R=-H).(2)3-Diethyl malonate hydrazine quinolone derivatives(K1?6)were prepared from 4-aniline derivatives by five steps.All of the six novel ligands showed strong green fluorescence.The fluorescence performs the best in the polar proton solvents,and the fluorescence emission peaks were red-shifted with the polarity increase.The optimal concentration of the six ligands was 50 ?M,K6(R=-COOCH3)has the best fluorescence performance under optimal solvent and concentration,and the fluorescence quantum yield is 0.317.The ligands K1?6 were coordinated with Eu3+to obtain the corresponding rare earth complexes.The general formula can be denoted as EuK1?6(NO3)3·2H2O.The target Eu3+complexes showed the characteristic red light,and the fluorescence performance was affected by the substituent groups in the ligands as EuK6(NO3)3·ZHZO(R=-COOCH3)>EuK5(NO3)3·2H2O(R=-C1)>EuK4(NO3)3·2H2O(R=-Br)>EuK3(NO3)3.2H2O(R=-OCH3)>EuK2(NO3)3.2H2O(R=-CH3)>EuK1(NO3)3·2H2O(R=-H).The ligand K6 which has the best fluorescence performance was selected to be coupled with BSA,and the coupling result was verified by UV.The fluorescence spectra showed that K6-BSA still had strong green fluorescence,indicating that the novel 2-quinolone derivatives K1?6 have great application prospect in fluorescence marker,and had extremely high application value in the detection of protein.