Polydimethylsiloxane core–polycaprolactone shell nanofibers as biocompatible, real-time oxygen sensors

Real-time, continuous monitoring of local oxygen contents at the cellular level is desirable both for the study of cancer cell biology and in tissue engineering. In this paper, we report the successful fabrication of polydimethylsiloxane (PDMS) nanofibers containing oxygen-sensitive probes by electrospinning and the applications of these fibers as optical oxygen sensors for both gaseous and dissolved oxygen. A protective ‘shell’ layer of polycaprolactone (PCL) not only maintains the fiber morphology of PDMS during the slow curing process but also provides more biocompatible surfaces. Once this strategy was perfected, tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) (Ru(dpp)) and platinum octaethylporphyrin (PtOEP) were dissolved in the PDMS core and the resulting sensing performance established. These new core–shell sensors containing different sensitivity probes showed slight variations in oxygen response but all exhibited excellent Stern–Volmer linearity. Due in part to the porous nature of the fibers and the excellent oxygen permeability of PDMS, the new sensors show faster response (<0.5 s)-4–10 times faster than previous reports–than conventional 2D film-based oxygen sensors. Such core–shell fibers are readily integrated into standard cell culture plates or bioreactors. The photostability of these nanofiber-based sensors was also assessed. Culture of glioma cell lines (CNS1, U251) and glioma-derived primary cells (GBM34) revealed negligible differences in biological behavior suggesting that the presence of the porphyrin dyes within the core carries with it no strong cytotoxic effects. The unique combination of demonstrated biocompatibility due to the PCL ‘shell’ and the excellent oxygen transparency of the PDMS core makes this particular sensing platform promising for sensing in the context of biological environments.