Synthesis And Application Of Lanthanide Functionalized Self-assembled Micelle Nanomaterials

Lanthanide ions have unique fluorescence properties,such as inherent narrow-band fluorescence,long fluorescence lifetime,and large Stokes shift.Due to the f-f transition of the lanthanide ions is Laporte forbidden,the antenna ligands are required to transfer energy to the lanthanide ions,then the sensitized lanthanide ions can emit fluorescence.Therefore,the multiple functional properties of lanthanide complexes can be obtained through designing the ligand structure.However,the drawbacks of single lanthanide complex are poor water solubility,poor light stability,and weak mechanical strength,which limit its application.In recent years,lanthanide complex nanocomposites which are formed by nanomaterials as matrix and lanthanide complexes have become a new research trend.Lanthanide complex nanocomposites not only remain the excellent properties of nanomaterials and lanthanide complexes,but also effectively improve the defects of lanthanide complexes,thus realizing the multifunctionality of lanthanide composite nanomaterials.Therefore,Lanthanide functionalized composite nanomaterials have important appilcation value in bioimaging,small molecule probes,cancer diagnosis and treatment,and drug transportation.In this type of multifunctional composite naonomaterial,the supramolecular self-assembled materials formed by the self-assembly of amphiphilic monomers have become a focus for researchers as a result of their unique properties.Micelle as one of the important structures constituted in aqueous solutions have attracted extensive attention.It has good water solubility,favorable biocompatibility and easy surface functionalization and is used in the field of light trapping,bioimaging,drug transport and small molecule identification etc.In this paper,an amphiphilic ligand which contain?-diketone structure was designed and synthesized.The amphiphilic ligand can coordinate with lanthanide ion and assemble in aqueous solution to form lanthanide functionalized micelle nanoparticle.The morphology and composition of the micelle nanoparticles were characterized by surface tension,UV-vis and FT-IR spectrum,dynamic light scattering and transmission electron microscopy.Then,we study the fluorescence,detection performance and practical potential applications of lanthanide functionalized micelle nanoparticles.The results have shown that the lanthanide functionalized micelle probe can high sensitive and selective detection of biomarker with.Based on this work,we can continue to design and synthesize new two-photon lanthanide functionalized micelle probe,and it be used for FRET?fluorescence resonance energy transfer?ratiometric detection of biomolecule.This work provides a feasible strategy for the design of novel lanthanide functionalized supramolecular nanomaterials and has important theoretical significance for the study of lanthanide functionalized nanomaterials.This paper is divided into there parts:Chapter 1:The paper reviewed the research progress of lanthanide complexes and lanthanide functionalized composite nanomaterials in the field of fluorescence sensors.Chapter 2:It was studied the self-assembly of lanthanide functionalized micelle nanoprobe and its application in the detection of anthrax spore biomarker.An amphophilic ligand contained?-diketone was designed and synthesized.The ligand L coordinated with lanthanide ion(Tb³⁺)to give amphiphilic lanthanide complex.The lanthanide functionalized micelle nanoprobe is obtained by self-assembly in aqueous solution and a fluorophore is loaded in the hydrophobic cavity as a fluorescence reference,so that a ratiometric fluroescence response can be generated.Based on the ligand exchange reaction of lanthanide ions,the micelle nanoprobe exhibit excellent selectivity and sensitivity to anthrax spore biomarker,pyridinedicarboxylic acid?DPA?.When different concentration of DPA was added into the aqueous of lanthanide functionalized micelle,the luminescence of Tb³⁺ion in the micelle enhanced linearly and the fluorescence of FR remained constant.The lanthanide functionalized micelle nanoprobe can response to DPA within seconds,and the detection range can be easily changed by adjusting the concentration of lanthanide functionalized micelle.The silica gel plate impregnated with the micelle nanoprobe can be used as test paper for detection of DPA.Chapter 3:A new fluorescent probe was synthesized which can used for visual detection of cysteine.It was studied of the response and the selectivity of probe to cysteine.The probe can specifically detect cysteine and can be used to detect intracellular cysteine concentration.