RESUMO
Image contrast is often limited by background autofluorescence in steady-state bioimaging microscopy. Upconversion bioimaging can overcome this by shifting the emission lifetime and wavelength beyond the autofluorescence window. Here we demonstrate the first example of triplet-triplet annihilation upconversion (TTA-UC) based lifetime imaging microscopy. A new class of ultra-small nanoparticle (NP) probes based on TTA-UC chromophores encapsulated in an organic-inorganic host has been synthesised. The NPs exhibit bright UC emission (400-500â nm) in aerated aqueous media with a UC lifetime of ≈1â µs, excellent colloidal stability and little cytotoxicity. Proof-of-concept demonstration of TTA-UC lifetime imaging using these NPs shows that the long-lived anti-Stokes emission is easily discriminable from typical autofluorescence. Moreover, fluctuations in the UC lifetime can be used to map local oxygen diffusion across the subcellular structure. Our TTA-UC NPs are highly promising stains for lifetime imaging microscopy, affording excellent image contrast and potential for oxygen mapping that is ripe for further exploitation.
RESUMO
Triplet-triplet-annihilation upconversion (TTA-UC) has attracted significant attention as an approach to harvest low energy solar photons that cannot be captured by conventional photovoltaic devices. However, device integration requires the design of solid-state TTA-UC materials that combine high upconversion efficiency with long term stability. Herein, we report an efficient solid-state TTA-UC system based on organic-inorganic hybrid polymers known as ureasils as hosts for the archetypal sensitiser/emitter pair of palladium(ii) octaethylporphyrin and diphenylanthracene. The role of the ureasil structure on the TTA-UC performance was probed by varying the branching and molecular weight of the organic precursor to tune the structural, mechanical, and thermal properties. Solid-state green-to-blue UC quantum yields of up to 1.86% were observed under ambient conditions. Notably, depending on the ureasil structure, UC emission could be retained for >70 days without any special treatment, including deoxygenation. Detailed analysis of the structure-function trends revealed that while a low glass transition temperature is required to promote TTA-UC molecular collisions, a higher inorganic content is the primary factor that determines the UC efficiency and stability, due to the inherent oxygen barrier provided by the silica nanodomains.
RESUMO
Triplet-triplet annihilation upconversion (TTA-UC) is a process by which a lower energy photon can be upconverted to a higher energy state. The incorporation of TTA-UC materials into solid-state hosts has enabled advances in solar energy and many other applications. The choice of host system is, however, far from trivial and often calls for a careful compromise between characteristics such as high molecular mobility, low oxygen diffusion, and high material stability, factors that often contradict one another. Here, we evaluate these challenges in the context of the state-of-the-art of primarily polymer hosts and the advantages they hold in terms of material selection and tunability of their diffusion or mechanical or thermal properties. We encourage more collaborative research between polymer scientists and photophysicists in order to further optimize the current systems and outline our thoughts for the future direction of the field.