title: Oxygen Sensing Difluoroboron β-Diketonate Polylactide Materials with Tunable Dynamic Ranges for Wound Imaging.
abstract: Difluoroboron β-diketonate poly(lactic acid) materials exhibit both fluorescence (F) and oxygen sensitive room-temperature phosphorescence (RTP). Introduction of halide heavy atoms (Br and I) is an effective strategy to control the oxygen sensitivity in these materials. A series of naphthyl-phenyl (nbm) dye derivatives with hydrogen, bromide and iodide substituents were prepared for comparison. As nanoparticles, the hydrogen derivative was hypersensitive to oxygen (0-0.3%), while the bromide analogue was suited for hypoxia detection (0-3% O2). The iodo derivative, BF2nbm(I)PLA, showed excellent F to RTP peak separation and an 0-100% oxygen sensitivity range unprecedented for metal-free RTP emitting materials. Due to the dual emission and unconventionally long RTP lifetimes of these O2sensing materials, a portable, cost-effective camera was used to quantify oxygen levels via lifetime and red/green/blue (RGB) ratiometry. The hypersensitive H dye was well matched to lifetime detection, simultaneous lifetime and ratiometric imaging was possible for the bromide analogue, whereas the iodide material, with intense RTP emission and a shorter lifetime, was suited for RGB ratiometry. To demonstrate the prospects of this camera/material design combination for bioimaging, iodide boron dye-PLA nanoparticles were applied to a murine wound model to detect oxygen levels. Surprisingly, wound oxygen imaging was achieved without covering (i.e. without isolating from ambient conditions, air). Additionally, would healing was monitored via wound size reduction and associated oxygen recovery, from hypoxic to normoxic. These single-component materials provide a simple tunable platform for biological oxygen sensing that can be deployed to spatially resolve oxygen in a variety of environments.
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904.
authors.forename: Christopher A
authors.initials: CA
authors.lastname: DeRosa
authors.affiliation: Department of Biomedical Engineering, University of Virginia, Charlottesville, Virginia 22908.
authors.forename: Scott A
authors.initials: SA
authors.lastname: Seaman
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904.
authors.forename: Alexander S
authors.initials: AS
authors.lastname: Mathew
authors.affiliation: Department of Biomedical Engineering, University of Virginia, Charlottesville, Virginia 22908.
authors.forename: Catherine M
authors.initials: CM
authors.lastname: Gorick
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904.
authors.forename: Ziyi
authors.initials: Z
authors.lastname: Fan
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904.
authors.forename: James N
authors.initials: JN
authors.lastname: Demas
authors.affiliation: Department of Biomedical Engineering, University of Virginia, Charlottesville, Virginia 22908.
authors.forename: Shayn M
authors.initials: SM
authors.lastname: Peirce
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904; Department of Biomedical Engineering, University of Virginia, Charlottesville, Virginia 22908.
authors.forename: Cassandra L
authors.initials: CL
authors.lastname: Fraser
keywords: Difluoroboron β–diketonate complexes; RGB camera imaging; fluorescence; poly(lactic acid); ratiometric oxygen sensing; room-temperature phosphorescence; wound healing