Extracellular oxygen sensors based on PtTFPP and four-arm block copolymers

Three four-arm amphiphilic block copolymers with different chain lengths, consisting of a hydrophilic chain of polyethylene glycol (PEG) and hydrophobic segment of polycaprolactam (PCL), were synthesized and used to encapsulate the high-efficient and hydrophobic oxygen probe of platinum(II)-5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorophenyl)-porphyrin (PtTFPP) to form polymer micelles. This approach enabled the use of PtTFPP in aqueous solution for biosensing. Experimental results demonstrated that the particle sizes of these nano-oxygen sensors between 40.0 and 203.8 nm depend on the structures of block copolymers. PtTFPP in these micelles showed an effective quantum yield under nitrogen environment, ranging from 0.06 to 0.159. The new sensors are suitable for analyzing dissolved oxygen concentrations in the range of 0.04-39.3 mg/L by using the linear Stern-Volmer equation at room temperature. In addition, it has been shown that these sensors are capable of in situ monitoring the dissolved oxygens in the culture medium of E. coli and Romas cells during the respiration process, and distinguishing the drug activity of antibiotic ampicillin from that of antimycin A. This study showed that the use of these nanostructured multi-arm block copolymer micelles can achieve efficient biological applications without specific structural modification of the hydrophobic PtTFPP probe, which is expected to have broad prospects.