Nanoprobes are advantageous over small molecular probes in sensitivity but most luminescence molecules used to construct nanoprobes often suffer from an aggregation-caused quenching effect. Herein, we rationally designed a small molecular probe Cys(StBu)-Lys(Ru(bpy)32+)-CBT (1) which "smartly" self-assembled into nanoparticles 1-NPs inside cells with non-quenched, persistent phosphorescence. Employing this property, we successfully applied 1 for long-term sensing of biothiol activity in living HepG2 cells and tumors. We envision that, by modifying the amino group with an enzyme substrate, our probe 1 could be further developed for sensing intracellular enzyme activity with non-quenched, persistent phosphorescence.
Treatment of the 2,5-bis(2'-pyridyl)pyrrolato (PDP) anion with {Ru(COD)Cl} in THF readily yielded [Ru(PDP)(COD)Cl] (1) in almost quantitative yield. Anion metathesis of 1 in organic solvent by NO and OTf (OTf = triflato) gave [Ru(PDP)(COD)(NO)] (2) and [Ru(PDP)(COD)(OTf)] (3), and in aqueous solution by BF and PF afforded aqueous complexes [Ru(PDP)(COD)(HO)](BF) (4+·BF) and [Ru(PDP)(COD)(HO)](PF) (4+·PF), respectively. Treatment of 1 with PhICl in CHCl afforded 5 with halogenated pyrrole. These complexes exhibit similar structure, including one Ru(ii) atom, one 2,5-bis(2'-pyridyl)pyrrole and one monodentate anion or aqua ligand. Each Ru(ii) tightly binds to three adjacent coplanar sites of PDP ligand to form a meridional configuration. Complex 1 with NaIO as the oxidant in EtOAc-CHCN-HO (ratio = 3 : 1 : 2) proved to be highly effective in the catalytic oxidation of olefins to carbonyl products.
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