Synthesis Of Micro-nano Scale Metal-Organic Frameworks(MOFs) And Its Application In Detection, Sensing And Biological Medicine

The chemistry of organic-inorganic coordination polymers and supramolecular complexes has recently become an active area of increasing interest internationally.The study of coordination-driven self-assembled discrete and polymeric metal-organic frameworks(MOFs) is a very active interdisciplinary research area. These metal-organic assemblies have intriguing structures and applications as gas storage,smart optoelectronic, magnetic, and catalytic materials. Reduced to micro-nano scale,these metal-organic supramolecular assemblies have a better application prospect used in separation, enrichment and detection, and expanding its application field in heterogeneous catalysis, analytical chemistry, environment science and life science. In this thesis, a series of micro-nano scale porous metal-organic frameworks were synthesized, and its application in aromatic hydrocarbon enrichment and detection,oxidation of benzyl alcohols and condensation of aromatic aldehydes, fluorescent probe of bioactive molecules and cells confocal imaging, targeted drug delivery and release in vitro/vivo were investigated.Ⅰ. Five micro-nano MOFs including Cd-MOF, Zn-MOF, Cu-MOF, Ui O-66 and Ui O-68 were prepared, the smallest size of which is 30 nm. The different size and shape of these five MOFs were studied, which is helpful for exploring its application.Ⅱ. The micro-nano scale porous Cd-MOF was prepared by solvent permeation with good thermal stability and chemical stability in aqueous solution, which was successfully fabricated to the solid-phase microextraction(SPME), exhibiting high sensitivity and selectivity towards volatile benzene, toluene, o-, m-, p-xylene,ethylbenzene(termed as BTEX). The limits of detection for BTEX are 0.01-0.001μg L-1, which was used to detect the BTEX content in seawater.Ⅲ. A bifunctional micro-nano scale heterogeneous catalyst Pd(0)@Ui O-68-AP was prepared, it exhibits a typical heterogeneous catalytic nature, which can be catalyst to facilitate benzyl alcohol oxidation reaction in air and aromatic aldehydes condensation reaction under relative mild conditions with the excellent conversion((29) 99%) and selectivity((29) 99%). The catalyst Pd(0)@Ui O-68-AP can be used more than five times.Ⅳ. Two micro-nano scale Ui O-MOFs named Mi-Ui O-66、Mi-Ui O-67 were prepared and fully characterized by powdered X-ray diffraction, transmission electron microscopy, scanning electron microscope and BET. They are shown to be highly porous and very stable in aqueous media, and can sensitively detect Cys and GSH over other physiologically relevant amino acids for the first kind of MOFs. They showed the most sensitivity for 10-11 M, and their fluorescence imaging in living cells was well demonstrated.Ⅴ Micro-nano scale Mi-Ui O-68 was prepared and fully characterized by powdered X-ray diffraction, transmission electron microscopy, scanning electron microscope and DLS with a higher stability in biosystem. Mi-Ui O-68 loaded with Dox with colour and fluorescence changed, and its fluorescence imaging in living cells was well demonstrated. The MTT of Mi-Ui O-68、Dox@Mi-Ui O-68 and Dox@Mi-Ui O-68-FA based on cancer cell were investigated.In this thesis, a series of micro-nano scale porous metal-organic frameworks were synthesized, and its application in aromatic hydrocarbon enrichment and detection,oxidation of benzyl alcohols and condensation of aromatic aldehydes, fluorescent probe of bioactive molecules and cells confocal imaging, targeted drug delivery and release in vitro were investigated.