Experimental Verification of the Accuracy of Oxygen-Varying Correlated Fluorescence for Determining the Quenching Constant KSV

The oxygen-varying correlated fluorescence provides an effective strategy to gain the quenching constant KSV for a non-phosphorescent system. Owing to the absence of detectable phosphorescence emission in general optical spectroscopy, the facticity of this method has never been verified. Here, the correct way to determine KSV by oxygen-varying correlated fluorescence was systematically studied in detail. We selected gadolinium protoporphyrin IX (Gd-PpIX) to establish a fluorescence and phosphorescence dual emission system. Then, KSV of Gd-PpIX can be obtained by the change of fluorescence intensity (IF) with oxygen concentration using the method of correlated fluorescence at intense pump power; meanwhile, the value can also be determined from the relationship of the phosphorescence intensity ratio and oxygen content by the Stern-Volmer equation under relatively low power density. It was found that the KSV values obtained by the above two methods were 12.2(1) and 11.9(7) kPa-1, respectively. Our results successfully verified the accuracy of oxygen-varying correlated fluorescence for determining the KSV by the phosphorescence property and fluorescence saturation of Gd-PpIX.