Light-switch probes,where the probe only emits light on binding to its target,are highly attractive in bioimaging as they provide for outstanding contrast,especially in the interrogation of a discrete and dynamic dist...Light-switch probes,where the probe only emits light on binding to its target,are highly attractive in bioimaging as they provide for outstanding contrast,especially in the interrogation of a discrete and dynamic distributed structure like G-quadruplex DNA.Here,we examine the photophysical properties of a G-quadruplex(G4)selective probe comprising a light-switch Ru_((II))dipyridylphenazine complex coassembled with the well-known G4 selective ligand PDC3;[Ru(phen)_(2)PDC3]^(4+)(RuPDC3),using femtosecond and nanosecond transient absorption spectroscopy,complemented by steady-state spectroscopy and spectro-electrochemistry.We compared the photophysics of RuPDC3 with that of a well-known photo-switch[Ru(bpy)_(2)(dppz)]^(2+),Rudppz,and observed marked differences in their behaviours.Whereas in Rudppz,the ^(3)MLCT state is either localized on the phenanthroline or the phenazine unit,we show that in RuPDC3,this state has charge delocalised over the entire PDC3 unit.We then compared the ultrafast dynamics of this complex with Rudppz when associated with duplex and G4 DNA of different topologies and observed notable differences in trends in the exited-state dynamics in both RuPDC3 and Rudppz with G4 for the first time.RuPDC3 shows greater variation in excited-state dynamics with G4 topology and offers the prospect of elucidation of topology by ultrafast imaging.展开更多
基金Science Foundation Ireland under grant number[19/FFP/6428]the Irish Research Council for funding.
文摘Light-switch probes,where the probe only emits light on binding to its target,are highly attractive in bioimaging as they provide for outstanding contrast,especially in the interrogation of a discrete and dynamic distributed structure like G-quadruplex DNA.Here,we examine the photophysical properties of a G-quadruplex(G4)selective probe comprising a light-switch Ru_((II))dipyridylphenazine complex coassembled with the well-known G4 selective ligand PDC3;[Ru(phen)_(2)PDC3]^(4+)(RuPDC3),using femtosecond and nanosecond transient absorption spectroscopy,complemented by steady-state spectroscopy and spectro-electrochemistry.We compared the photophysics of RuPDC3 with that of a well-known photo-switch[Ru(bpy)_(2)(dppz)]^(2+),Rudppz,and observed marked differences in their behaviours.Whereas in Rudppz,the ^(3)MLCT state is either localized on the phenanthroline or the phenazine unit,we show that in RuPDC3,this state has charge delocalised over the entire PDC3 unit.We then compared the ultrafast dynamics of this complex with Rudppz when associated with duplex and G4 DNA of different topologies and observed notable differences in trends in the exited-state dynamics in both RuPDC3 and Rudppz with G4 for the first time.RuPDC3 shows greater variation in excited-state dynamics with G4 topology and offers the prospect of elucidation of topology by ultrafast imaging.
