In this work, the synthesis, structural and photophysical characterization of six phosphorescent H 2 O-soluble Pt(II) complexes are reported while addressing their emission maxima, photoluminescence quantum yields (Φ L ), lifetimes (τ), aggregation tendency, and microenvironment sensitivity as a function of the substitution pattern on the main tridentate luminophore. Different ancillary ligands, namely, a trisulfonated phosphane and maltohexaose-conjugated pyridines (with or without amide bridges), were introduced and evaluated for the realization of switch-on-photoluminescent labels reporting on the microenvironment sensed in biofilms of Gram + and Gram − models, namely, Staphylococcus aureus and Escherichia coli. With the aid of confocal luminescence micro(spectro)scopy, we observed that selected complexes specifically interact with the biofilms while leaving planktonic cells unlabeled. By using photoluminescence lifetime imaging microscopy, excited-state lifetimes within S. aureus biofilms were measured. The photoluminescence intensities were drastically boosted, and the excited state lifetimes were significantly prolonged upon binding to the viscous biofilm matrix, mainly due to the suppression of radiationless deactivation pathways upon shielding from physical quenching processes, such as interactions with solvent molecules and 3 O 2 . The best performances were attained for non-aggregating complexes with maltohexaose targeting units and without amide bridges. Notably, in the absence of the maltodextrin, a hydrophobic adamantyl moiety suffices to attain a sizeable labeling capacity. Moreover, photoluminescence studies showed that selected complexes can also effectively interact with E. coli biofilms, where the bacterial cells are able to partially uptake the maltodextrin-based agents. In summary, the herein introduced concepts enable the development of specific biofilm reporters providing spatial resolution as well as lifetime-and spectrum-based readouts. Considering that most theragnostic agents reported so far mainly address metabolically active bacteria at the surface of biofilms but without reaching cells deeply immersed in the matrix, a new platform with a clear structure-property correlation is provided for the early detection of such bacterial arrays.
Efficient shielding of phosphorescent transition metal complexes against diffusion-controlled collisional quenching by triplet molecular dioxygen as well as reduction of microenvironment-related radiationless deactivation pathways is crucial for their applications in bioimaging and optoelectronics. In this report, we present a straightforward yet efficient approach to safeguard emissive triplet states from external influences by adsorbing phosphorescent Pt(II) complexes onto a layered nanoclay, namely Laponite. These hybrids facilitate the dispersion of otherwise insoluble transition metal complexes in aqueous media while shielding them from physical quenching. Self-assembly of the nanoclay and intermolecular stacking between molecules adsorbed at different nanodisc units are mirrored in the photophysical, colloidal, and morphological properties of the hybrids, which were herein characterized by steady-state and time-resolved photoluminescence spectroscopy, dynamic light scattering, and atomic force microscopy. We also show that the hybrids are noncytotoxic and can be exploited as luminescent reporters in spectrally resolved phosphorescence lifetime imaging implemented by confocal optical microscopy.
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