Thermal stabilisation of squaraine dyes by encapsulation in a rotaxane

Encapsulation of a squaraine dye in a rotaxane structure renders the dye that normally start decomposing at 100 °C stable above 250 °C. This thermal stabilisation makes new applications possible, and we demonstrate how the squaraine rotaxane can mediate laser welding of polyethylene.

Enhanced Squaraine Rotaxane Endoperoxide Chemiluminescence in Acidic Alcohols

Squaraine rotaxane endoperoxides (SREPs) are storable chemiluminescent compounds that undergo a clean cycloreversion reaction that releases singlet oxygen and emits near-infrared light when warmed to body temperature. This study examined the effect of solvent on SREP chemiluminescence intensity and found that acidic alcohols, such as 2,2,2-trifluoroethanol, α-(trifluoromethyl)benzyl alcohol, and 1,1,1,3,3,3-hexafluoroisopropanol, greatly increased chemiluminescence. In contrast, aprotic solvents, such as trifluoroethylmethyl ether, had no effect. The interlocked rotaxane structure was necessary as no chemiluminescence was observed when the experiments were conducted with samples containing a mixture of the two non-interlocked components (squaraine thread and macrocycle endoperoxide). Spectroscopic analyses of the enhanced SREP chemiluminescent reactions showed a mixture of products. In addition to the expected squaraine rotaxane product caused by cycloreversion of the endoperoxide, a diol derivative was isolated. The results are consistent with an endoperoxide O–O bond cleavage process that is promoted by the hydrogen bonding solvent and produces light emission from a squaraine excited state.

Singlet Oxygen Release and Cell Toxicity of a Chemiluminescent Squaraine Rotaxane Dye: Implications for Molecular Imaging

The water soluble tetraguanidinium squaraine rotaxane 2 was prepared and photoconverted to its corresponding squaraine rotaxane endoperoxide (SREP), 2EP. As expected, 2EP undergoes a thermal cycloreversion reaction that releases 60 ± 4% singlet oxygen and produces near-infrared emission in aqueous solution. Cell toxicity assays in the dark, using human and bacterial cell cultures, showed that 2EP (up to 20 µM) is no more toxic than its parent 2. This suggests that SREP-derived imaging probes are not likely to exhibit a significant toxicity effect due to the slow release of stoichiometric amounts of singlet oxygen. Additional photosensitization experiments showed that tetraguanidinium squaraine rotaxane 2 is a weak photosensitizer, but nonetheless, red light irradiation of cell cultures that were pre-incubated with 2 (>3 µM) produced moderate phototoxicity. Fluorescence microscopy studies attribute the phototoxicity of 2 to its ability to penetrate into the cell cytosol. The implications of these results are discussed in the context of effective methods to activate SREP as chemiluminescent probes for in vivo optical molecular imaging.