Research On Construction And Application Of Zirconium-Based Porous Materials

In recent years,the research of porous materials has developed rapidly.As an important class of functional materials,due to their high specific surface area,regular pore structures and adjustable active centers and functional units,these materials exhibit extremely important applications in the fields of petrochemical industry,fine chemical industry and daily chemical industry as adsorption,separation,catalysis and photoelectric materials.In recent years,porous functional materials have also played an increasingly important role in biomedical fields,including chemical sensing,drug delivery and bioimaging.Metal-organic framework materials have received extensive attention in recent years,among which,metal-organic-frameworks(MOFs)with fluorescent properties has been proved to be an excellent fluorescent probe for sensitive detection and imaging of biologically active molecules.However,this MOFs fluorescent probe still has some unsolved problems,such as biological autofluorescence interference and poor tissue penetration.Compared with traditional single photon fluorescence probes,two-photon fluorescence probes have attracted more and more attention in biomedical research recently due to the intrinsic advantages originated from simultaneous absorption of two low energy photons,such as lower excitation energy,less photodamage,deeper tissue penetration,smaller interference of spontaneous fluorescence and higher imaging resolution.Polydopamine(PDA)nanoparticles have shown great application prospects in biomedicine,especially in cancer therapy due to their excellent photothermal properties,good biocompatibility,and unique chemical structure.In addition to nonporous PDA materials,porous particles with extensive internal spaces can not only provide complex intraparticle morphologies and structures,but also exhibit new or improved properties.The preparation of novel mesoporous PDA nanoparticles is of great significance for the development of novel carriers for nanoencapsulation,high-quality delivery nanosystems,and complex assembly structures.In this thesis,two kinds of porous materials,metal-organic framework materials and mesoporous polydopamine,have been constructed,and their applications in biosensor,photothermal therapy and drug delivery were studied.The main contents include the following two parts:1.Using a convenient method that can avoid complicated post modification of ligands,we for the first time developed a novel sensitive two-photon MOF fluorescence probe that can effectively monitor the fluctuation of endogenous glutathione(GSH)level in living cells.The detection limit of this sensitive probe is as low as 87 n M,and the tissue penetration depth increased to 170 nm.At the same time,the relationship between the chemotherapeutic drug doxorubicin resistance and GSH concentration changes in different tumor cells and normal cells was successfully evaluated in real time using this probe.2.Using metal-organic framework UiO-66 as template,we successfully prepared nano mesoporous MPDA particles.The anti-inflammatory drugs were then encapsulated in MPDA with a loading of 27.9 wt%,and further modified with hyaluronic acid to obtain the final product MPFH.MPFH can specifically target tumor cells for near-infrared laser-triggered photothermal therapy(PTT),while light-induced controllable MPDA drug release effectively inhibited PTT-induced inflammatory response.