Tailoring Oxygen Sensitivity with Halide Substitution in Difluoroboron Dibenzoylmethane Polylactide Materials

DeRosa, Christopher A.; Kerr, Caroline P.; Fan, Ziyi; Kołpaczyńska, Milena; Mathew, Alexander S.; Evans, Ruffin E.; Zhang, Guoqing; Fraser, Cassandra L.

doi:10.1021/acsami.5b07126

Cited by 73 publications

(59 citation statements)

References 73 publications

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“…1,2 Difluoroboron β-diketonate (BF 2 bdk) complexes are of particular interest due to their impressive emission properties and the facile synthesis of β-diketonates via Claisen condensation from a variety of commercially available ketones and esters. 1,3-7 Desirable properties of BF 2 bdks include high extinction coefficients, 8-10 high quantum yields, 8-10 two-photon absorption cross-sections, 8,11 a range of emission colors in solution and the solid state, 10,12 solvatochromism, 4 and the ability to impart significant intramolecular charge transfer (ICT) character in unsymmetrical analogues. 13 Previously we reported the unique mechanochromic luminescent (ML) properties 6,7,12,14,15 of BF 2 bdk dyes as well as their ability to act as dual-emissive ratiometric oxygen sensors in polymer media.…”

Section: Introductionmentioning

confidence: 99%

Stimuli responsive furan and thiophene substituted difluoroboron β-diketonate materials

Morris

Butler

Kołpaczyńska

et al. 2017

Mater. Chem. Front.

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Difluoroboron β-diketonate (BF2bdk) compounds exhibit solid-state switchable luminescence under excitation by UV light. This property is usually manifested as a blue-shift in emission when dye films are thermally annealed followed by a red-shift in response to mechanical shear (i.e. mechanochromic luminescence). Here we report thiophene and furan heterocycle-substituted dyes bearing short methoxy and long dodecyloxy chain substituents. Optical properties of the dyes were investigated in solution, pristine powders, and films on paper and glass. The structural and thermal properties of the dyes were also investigated by powder x-ray diffraction (XRD) and differential scanning calorimetry (DSC), respectively. The methoxy-substituted dyes exhibited neither thermal nor mechano-responsive behavior, however, addition of a longer C12 alkoxyl chain substituent resulted in stimuli-responsive behavior. The furan and thiophene dodecyloxy-substituted dyes both exhibit high-contrast reversible luminescence switching between crystalline, blue-shifted and amorphous red-shifted emissive states. For the furan dye, gentle heating produced a green emissive form while melting followed by rapid cooling produced an orange emissive form. The thiophene dye, on the other hand, exhibited blue-shifted emission when annealed below its melting temperature and red-shifted emission when smeared with a cotton swab (mechanochromic luminescence). These transformations for both dyes were found to be completely reversible, making them potential candidates for applications requiring reusable, functional materials.

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Section: Introductionmentioning

confidence: 99%

Stimuli responsive furan and thiophene substituted difluoroboron β-diketonate materials

Morris

Butler

Kołpaczyńska

et al. 2017

Mater. Chem. Front.

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“…26 However, all blends showed a phosphorescence afterglow in an oxygen-free nitrogen atmosphere. The phosphorescence properties of the thienyl dyes displayed red-shifted emission with increasing conjugation length and donor ability, and showed an impressive range of colors from green to orange.…”

Section: Discussionmentioning

confidence: 94%

“…Large Stokes shifts, controllable oxygen sensitivity, and high color tunability make these single-component materials ideal candidates for oxygen sensing, especially for tumor hypoxia imaging. 18,24,26,27 …”

Section: Introductionmentioning

confidence: 99%

Thienyl Difluoroboron β-Diketonates in Solution and Polylactide Media

et al. 2016

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Difluoroboron β–diketonates have impressive optical properties in both solution and the solid state. In particular, both fluorescence and room-temperature phosphorescence are present when the dyes are confined to a rigid matrix, such as poly(lactic acid) (PLA). To expand current knowledge and color range capabilities of this unique type of multi-emitting chromophore, a series of thienyl-substituted BF2bdk complexes have been synthesized. The photophysical properties were investigated in methylene chloride solution and in the solid state as dye/PLA blends. By varying donor ability, i.e. methyl, phenyl, methoxyl, and thienyl substituents, and by changing the dye loading in the PLA media (0.1–10% dye loading) red-shifted emission was achieved, important for biological imaging applications. In dilute CH2Cl2 solution, complexes exhibited absorptions ranging from 350 – 420 nm, solid-state fluorescence in PLA ranging from 390 – 500 nm, and oxygen sensitive phosphorescence ranging from 540 – 585 nm in PLA blends. Promising candidates as dye/PLA blends serve as models for dyepolymer conjugates for application as biological oxygen nanoprobes.

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“…41 Furthermore, in a previous report we discovered higher MW polymers (>16 kDa) have larger fluorescence to room temperature phosphorescence (RTP) wavelength gaps, important for ratiometric oxygen quantification techniques, and they are more photostable (Figures S1–S5). 37,38 …”

Section: Resultsmentioning

confidence: 99%

“…36–39 First, it was necessary to increase the phosphorescence intensity by the heavy atom effect via introduction of bromide or iodide. 27,36–38 Secondly, for ratiometric sensing, ideally the fluorescence and phosphorescence peaks should be distinct, and the F/P intensity ratio must be optimized. 36,37 This was achieved through a combination of ligand modification and molecular weight (i.e dye loading) effects.…”

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Oxygen Sensing Difluoroboron β-Diketonate Polylactide Materials with Tunable Dynamic Ranges for Wound Imaging

et al. 2016

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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 O2 sensing 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.

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Tailoring Oxygen Sensitivity with Halide Substitution in Difluoroboron Dibenzoylmethane Polylactide Materials

Cited by 73 publications

References 73 publications

Stimuli responsive furan and thiophene substituted difluoroboron β-diketonate materials

Stimuli responsive furan and thiophene substituted difluoroboron β-diketonate materials

Thienyl Difluoroboron β-Diketonates in Solution and Polylactide Media

Oxygen Sensing Difluoroboron β-Diketonate Polylactide Materials with Tunable Dynamic Ranges for Wound Imaging

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