| Due to the advantages of large specific surface area,diverse coordination types and methods,and easy adjustment of morphology and performance,metal-organic frameworks(MOFs)nanoporous materials are widely used in gas storage and separation,catalysis,biosensors,and biomedical fields,etc.Among them,nickel-based MOFs have attracted widespread attention due to abundant coordination groups and good stability.In this paper,nickel-copper and nickel-cobalt bimetallic MOFs and composites of nickel-MOF and polymer are synthesized by hydrothermal methods.Based on the investigation of the formation mechanism of the bimetallic MOFs and nickel metal composite materials,the basic application properties of the bimetallic MOFs and nickel metal composite materials as biosensor sensitive membranes and anticancer drug nanocarriers were initially explored.It mainly includes the following three aspects:First,copper-nickel bimetallic MOFs were synthesized by a hydrothermal method,and their basic properties as biosensor sensitive membranes for the detection of protein tyrosine kinase(PTK7)and glioma cell(C6)for were investigated.Using Cu(NO3)2 and Ni(NO3)2 as metal precursors and 2,3,6,7,10,11-hexahydroxytriphenylene(HHTP)as an organic ligand,a new type of semiconductor bimetal Cu3Ni3-x(HHTP)2 MOFs two-dimensional nanosheet material was synthesized.Due to its graphene-like nanosheet structure,PTK7 targeting nucleic acid aptamers can be strongly immobilized on bimetallic Cu3Ni3-x(HHTP)2 MOFs.When used in detection of PTK7 and C6,it exhibits excellent electrochemical sensing performance.In the linear range of PTK concentration of 1 fg·mL-1-2 ng·mL-1,the limit of detection(LOD)is as low as 0.72 fg·mL-1;For the detection of live cell C6,LOD is 21 cell·mL-1 in the linear range is 100-1*105 cell·mL-1.Next,a co-precipitation method was used to synthesize a regular bimetal NiCo Prussian blue analog(NiCo PBA)to construct a multifunctional electrochemical aptamer sensor,which was used to detect carcinoembryonic antigen(CEA)and human large cell lung cancer cells(MCF-7).When the NiCoPBA-based biosensor is used for CEA detection,the LOD is 0.74 fg·mL-1 in the linear range of 1 fg·mL-1-5 ng·mL-1 and the LOD for MCF-7 detection is 47 cell·mL-1 in the range of 100-5*106 cell·mL-1.In addition,the aptamer sensor has excellent selectivity,stability,repeatability and reproducibility.Finally,the NiCo PBA material was modified by adding rare earth ion europium(Tb3+)and polyethylene glycol dimethacrylate(PEGMA)with fluorescent properties to obtain NiCo-PBA@Tb3+@PEGMA,which be exploxed as an anticancer drug carrier with excellent biocompatibility.The results show that the carrier has a drug loading rate of 88.7%as well as good pH responsiveness and drug sustained release performance When pH is 5,the drug release rate reaches 75%.In addition,the drug carrier displays a low cytotoxicity.When the drug carrier is incubated at a concentration of 200 μg·mL-1,the cell survival rate is as high as 82.5%.Finally,the vivo antitumor studies in tumor-bearing mice showed that nano-drug carriers could specifically recognize cancer cells After 8 days of administration,the tumor tissue in mice was significantly reduced Stained sections show that only a small amount of cancer cells are present in the administration group.It can be seen that obvious therapeutic effects have been achievedIn summary,this paper provides new ideas for MOFs and their composites in the field of early diagnosis and treatment of tumors,and expands the application scope of nickel-based MOFs materials in the biomedical field. |