Reversible Enzymatic Switching of the Oxidation State of a EuIII/II Complex Controls Relaxivity.
Sarson ET., Cooper SM., Sedgwick AC., Berger A-G., Twigger SA., Hammond EM., Vincent KA., Faulkner S.
We show that europium trisbipyridyl cryptate exhibits an electrochemically reversible EuIII/II redox couple at -360 mV vs the standard hydrogen electrode (SHE) and is susceptible to reduction or oxidation by a range of redox enzymes or biological small molecule redox agents. Modulation of the europium oxidation state can be used to achieve dramatic changes in the T1 relaxation time of bulk water in solutions containing these complexes: in the reduced form, the complex exhibits high relaxivity (3.08 mM-1 s-1 at 499.9 MHz) comparable with that of commercial MRI contrast media, while the oxidized form has negligible relaxivity, illustrating the scope for application in imaging reducing environments in biological systems.