Mechanism of oxygen-induced EPR line broadening in lithium phthalocyanine microcrystals

EPR oximetry has been recognized as an important tool for determining oxygen concentration in biological tissues, in vivo. The method relies on the use of oxygen-sensitive paramagnetic probes whose linewidth varies predictably, mostly linear, with oxygen concentration. Lithium phthalocyanine (LiPc) radical has emerged as the probe of choice due to its superior EPR sensitivity, oxygen response, and biocompatibility. However, there are certain limitations in the preparation of this material in a pure and usable form. In our efforts to improve the synthesis of this material for reliable use in oximetry applications, we developed microcrystalline particulates that showed several advantages over other probes. Despite its advantages, the probe shows linear response to pO₂ only in the range of 0-70mmHg, beyond which a saturation behavior is observed. The goal of this study was to understand the mechanism of the interaction of oxygen with LiPc in order to interpret the experimentally observed linewidths. We propose a dual-spin model in which the freely diffusing spins of LiPc are converted to fixed spins by adsorption of molecular oxygen. The proposed mechanism was verified from the effect of oxygenation/deoxygenation processes on the linewidth of LiPc. In summary, we demonstrated that adsorption of oxygen molecules on LiPc contributes to a nonlinear line-broadening effect. This understanding is important for the future design of new EPR oximetry probes.