Abstract
New amphiphilic star or multi-arm block copolymers with different structures were synthesized for enabling the use of hydrophobic oxygen probe of platinum (II)-tetrakis (pentafluorophenyl) porphyrin (PtTFPP) for bioanalysis. The amphiphilic star polymers were prepared through the Atom Transfer Radical Polymerization (ATRP) method by using hydrophilic 4-arm polyethylene glycol (4-arm-PEG) as an initiator. Among the five block copolymers, P1 series (P1a, P1b, and P1c) and P3 possess fluorine-containing moieties to improve the oxygen sensitivity with its excellent capacity to dissolve and carry oxygen. A polymer P2 without fluorine units was also synthesized for comparison. The structure-property relationship was investigated. Under nitrogen atmosphere, high quantum efficiency of PtTFPP in fluorine-containing micelles could reach to 22% and long lifetime could reach to 76 μs. One kind of representative PtTFPP-containing micelles was used to detect the respiration of Escherichia coli (E. coli) JM109 and macrophage cell J774A.1 by a high throughput plate reader. In vivo hypoxic imaging of tumor-bearing mice was also achieved successfully. This study demonstrated that using well-designed fluoropolymers to load PtTFPP could achieve high oxygen sensing properties, and long lifetime, showing the great capability for further in vivo sensing and imaging.
Highlights
Dissolved oxygen (DO) is crucial to environment, industry, life technology, and human health, etc
Considering the abundance of polymer structures, we extended this study to multi-arm block copolymers
Previously we reported that platinum (II)-tetrakis (pentafluorophenyl) porphyrin (PtTFPP) in micelles could achieve high quantum efficiency of 20–23%, through fluorescence resonance energy transfer (FRET) enhancement [27,30]
Summary
Dissolved oxygen (DO) is crucial to environment, industry, life technology, and human health, etc. There are several ways to detect dissolved oxygen such as Clark electrodes [10], Winkler titration [11] and optical sensors [12]. Phosphorescence based optical oxygen analysis makes up for the shortfalls of the first two methods with the following characters: (1) noninvasive and reversible sensing; (2) without oxygen consumption; (3) high sensitivity to oxygen with fast responses; and (4) capable for single cell level sensing. These properties gave huge potentials for phosphorescence oxygen sensing in biological application [15,16,17]
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