Excitation-Wavelength-Dependent Functionalities of Temporally Controlled Sensing and Generation of Singlet Oxygen by a Photoexcited State Engineered Rhodamine 6G-Anthracene Conjugate

The present study provides design guidance for unique multipotent molecules that sense and generate singlet oxygen (¹O₂). A rhodamine 6G-aminomethylanthracene-linked donor-acceptor molecule ( RA ) is designed and synthesized for demonstrating wavelength-dependent functionalities as follows; (i) RA acts as a conventional fluorogenic ¹O₂ sensor molecule like the commercially available reagent, singlet oxygen sensor green (SOSG), when it absorbs ultraviolet (UV)-visible light and reacts with ¹O₂. (ii) RA acts as a temporally controlled ¹O₂ sensing reagent under the longer wavelength (∼700 nm) photosensitization. RA enters an intermediate state after capturing ¹O₂ and does not become strongly fluorescent until it is exposed to UV, blue, or green light. (iii) RA acts as an efficient photosensitizer to generate ¹O₂ under green light illumination. The spin-orbit charge transfer mediated intersystem crossing (SOCT-ISC) process achieves this function, and RA shows a potential cancer-killing effect on pancreatic cancer cells. The wavelength-switchable functionalities in RA offer to promise molecular tools to apply ¹O₂ in a spatiotemporal manner.     

Constrictive Markov operators induced by Markov processes

Consider a constrictive Markov operator \(T:L^1(X, \Sigma , \mu ) \rightarrow L^1(X, \Sigma , \mu )\) defined on a finite measure space \((X, \Sigma , \mu )\). We give a necessary and sufficient condition for a constrictive Markov operator T which is an integral operator with stochastic kernel satisfying \(T\mathbf {1}_X=\mathbf {1}_X\).