Difluoroboron dibenzoylmethane-polylactide, BF 2 dbmPLA, a biocompatible polymerluminophore conjugate was fabricated as nanoparticles. Spherical particles <100 nm in size were generated via nanoprecipitation. Intense blue fluorescence, two-photon absorption, and long-lived room temperature phosphorescence (RTP) are retained in aqueous suspension. The nanoparticles were internalized by cells and visualized by fluorescence microscopy. Luminescent boron biomaterials show potential for imaging and sensing.Keywords boron dye; fluorescence; phosphorescence; poly(lactic acid) (PLA); nanoparticles Difluoroboron-based dyes, such as BODIPY 1 and β-diketonate derivatives, 2 exhibit large extinction coefficients, high emission quantum yields, large two-photon absorption crosssections, and in some cases, sensitivity to the surrounding medium. 3 These exceptional optical properties make them useful as imaging agents, 4 photosensitizers, 5 and sensors. 6 Often dyes are combined with material substrates to modulate properties, enhance stability, and reduce toxicity. Dye leaching with associated toxicity and ambiguity in imaging and sensing schemes can be minimized with dye-polymer conjugates versus blends. 7 For example, active agents such as Ru(II) complexes 8,9 or metalloporphyrins 10 are embedded in polymer matrices that act as protective shells and allow their use in biological contexts with increased stability and improved delivery 11,12 by passive 13,14 or active targeting. 15 Many multifunctional imaging and sensing agents combine controlled material synthesis with nanofabrication. 16,17 Nanoparticles based on luminescent dye conjugates and quantum dots 18 are used to label intracellular structures and pathways in fundamental studies as well as for therapeutic and diagnostic purposes. 19,20 Both fluorescence (singlet) and phosphorescence (triplet) emitters are widely used. Phosphorescence, in particular, is susceptible to oxygen quenching via triplet energy transfer, serving as the basis for oxygen sensing. 21-23 Good oxygen permeability and fast response time are important factors. Photodynamic therapy, on the other hand, utilizes photosensitizers in combination with oxygen or other quenchers to generate reactive species for selective tissue treatment. 24-26Previously we reported that when boron difluoride dibenzoylmethane (BF 2 dbm) is combined with poly(lactic acid) (PLA), a biocompatible polymer, 27 the intense blue fluorescence is retained and new properties emerge, namely temperature-sensitive delayed fluorescence and * Address correspondence to fraser@virginia.edu.
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RESULTS AND DISCUSSIONDifluoroboron dibenzoylmethane polylactide, BF 2 dbmPLA (Figure 1), was synthesized by ring opening polymerization of lactide using a hydroxyl-functionalized BF 2 dbm initiator and tin catalyst as previously described. 28 Nanoparticles were produced by the solvent displacement method (i.e., nanoprecipitation) 29,30 in which the polymer is dissolved in a solvent miscible with water (e.g., DMF) (oil phase),...