ABSTRACT
Photoswitching of bright fluorescent nanoparticles opens new possibilities for bioimaging with superior temporal and spatial resolution. However, efficient photoswitching of nanoparticles is hard to achieve using Förster resonance energy transfer (FRET) to a photochromic dye, because the particle size is usually larger than the Förster radius. Here, we propose to exploit the exciton diffusion within the FRET donor dyes to boost photoswitching efficiency in dye-doped polymer nanoparticles. To this end, we utilized bulky hydrophobic counterions that prevent self-quenching and favor communication of octadecyl rhodamine B dyes inside a polymer matrix of poly(D,L-lactide-co-glycolide). Among tested counterions, only perfluorinated tetraphenylborate that favors the exciton diffusion enables high photoswitching efficiency (on/off ratio â¼20). The switching improves with donor dye loading and requires only 0.1-0.3 wt % of a diphenylethene photochromic dye. Our nanoparticles were validated both in solution and at the single-particle level. The proposed concept paves the way to new efficient photoswitchable nanomaterials.
Subject(s)
Fluorescent Dyes/chemistry , Lactic Acid/chemistry , Nanoparticles/chemistry , Polyglycolic Acid/chemistry , Diffusion , Fluorescence Resonance Energy Transfer , Hydrophobic and Hydrophilic Interactions , Polylactic Acid-Polyglycolic Acid Copolymer , Rhodamines/chemistry , Tetraphenylborate/chemistryABSTRACT
We present a simple and versatile mechanism for the reversible photoswitching of dye-doped core-shell nanoparticles. Photochromic dithienylethenes are incorporated into the outer shell, close enough to the dyes entrapped in the core to efficiently quench them by energy transfer when photoconverted with UV light. The emission can be switched back on by irradiation with λ > 450 nm.
ABSTRACT
We present three recently developed photochromic fluorophores that are based on diarylethenes with elongated conjugated π-systems. The diarylethenes 1 and 3 can be switched from their open to their closed form with visible light. The diarylethenes 1 and 2 are covalently coupled to a standard rhodamine B-based fluorophore and act as photoswitchable resonance energy acceptors. By controlling their switching state, the fluorescence intensity of the dye can be modulated. The third compound 3 is a diarylethene that shows photoswitchable inherent fluorescence due to its stilbazolium-like structure. Ensemble experiments demonstrate that diarylethene-based photoswitches show superior characteristics regarding their switching performance, thermal stability and fatigue resistance. These attributes make them promising candidates for super-resolution imaging methods that are based on the determinate fluorescence switching of fluorophores between an off- and an on-state.
Subject(s)
Ethylenes/chemistry , Light , Ethylenes/chemical synthesis , Fluorescent Dyes/chemistry , Kinetics , Rhodamines/chemistry , Spectrophotometry, UltravioletABSTRACT
The syntheses and photochromic properties of six new photochromic dithienylethenes with differently substituted conjugated double bonds at the thiophene units are presented.
ABSTRACT
Fluorinated building blocks by C-F bond cleavage: Catalytic C-F activation reactions that give novel dioxaborolanes have been developed (see scheme). The reactions proceed at room temperature, and catalytic intermediates are presumably rhodium hydride and boryl species.