The photosensitized generation of reactive oxygen species, and particularly of singlet oxygen [O2 (a(1) Δg )], is the essence of photodynamic action exploited in photodynamic therapy. The ability to switch singlet oxygen generation on/off would be highly valuable, especially when it is linked to a cancer-related cellular parameter. Building on recent findings related to intersystem crossing efficiency, we designed a dimeric BODIPY dye with reduced symmetry, which is ineffective as a photosensitizer unless it is activated by a reaction with intracellular glutathione (GSH). The reaction alters the properties of both the ground and excited states, consequently enabling the efficient generation of singlet oxygen. Remarkably, the designed photosensitizer can discriminate between different concentrations of GSH in normal and cancer cells and thus remains inefficient as a photosensitizer inside a normal cell while being transformed into a lethal singlet oxygen source in cancer cells. This is the first demonstration of such a difference in the intracellular activity of a photosensitizer.
An entirely earth‐abundant chromophore‐relay water oxidation catalyst triad system, which is robust and efficient at neutral pH, is presented. The synthesis involves the coordination of a porphyrin derivative to a bridging Fe(CN)5 group, which is then reacted with Co ions to prepare a covalently linked chromophore–Prussian blue analogue assembly. Light‐driven water oxidation studies in the presence of an electron scavenger indicate that the triad is active and it maintains a steady activity for at least three hours. Transient absorption experiments and computational studies reveal that the Fe(CN)5 group is more than a linker as it takes part in electron‐transfer and co‐operates with porphyrin in the charge separation process.
Low lying electronic states of the highly fluorescent BODIPY (boron dipyrromethene, 1) and its nonemissive cousin dipyrrin (2) were investigated by state-of-the-art quantum chemical methods. The opposed luminescence of 1 and 2 is explained by discovering distinct structural and energetic features for the intersection of the ground and first excited singlet state potential energy surfaces, S(0) and S(1). In accessing the intersection region, a B-N σ-bond in 1 has to be broken-an energetically prohibitive change on the nonemissive decay channel. On the contrary, 2 is deactivated via an energetically accessible S(0)/S(1) intersection point. Details of S(0), S(1), S(2), and T(1) wave functions for various regions of the potential energy surfaces were described. Unnoted features for multidimensional vectors that represent S(0) → S(1) and S(0) → T(1) transitions are reported. These correlations regarding S(0) → S(1) and S(0) → T(1) multidimensional vectors were also shown to apply to two highly fluorescent molecules: indole and coumarin.
Triboelectric charging of insulators, also known as contact charging in which electrical charges develop on surfaces upon contact, is a significant problem that is especially critical for various industries such as polymers, pharmaceuticals, electronics, and space. Several methods of tribocharge mitigation exist in practice; however, none can reach the practicality of using light in the process. Here we show a light-controlled manipulation of triboelectric charges on common polymers, in which the tribocharges are mitigated upon illumination with appropriate wavelengths of light in presence of a mediator organic dye. Our method provides spatial and temporal control of mitigation of static charges on common polymer surfaces by a mechanism that involves photoexcitation of organic dyes, which also allows additional control using wavelength. This control over charge mitigation provides a way to manipulate macroscopic objects by tribocharging followed by light-controlled discharging.
Herein, we establish a simple synthetic strategy affording a heterogeneous, precious metal‐free, dye‐sensitized photoelectrode for water oxidation, which incorporates a Prussian blue (PB) structure for the sensitization of TiO2 and water oxidation catalysis. Our approach involves the use of a Fe(CN)5 bridging group not only as a cyanide precursor for the formation of a PB‐type structure but also as an electron shuttle between an organic chromophore and the catalytic center. The resulting hetero‐functional PB‐modified TiO2 electrode demonstrates a low‐cost and easy‐to‐construct photoanode, which exhibits favorable electron transfers with a remarkable excited state lifetime on the order of nanoseconds and an extended light absorption capacity of up to 500 nm. Our approach paves the way for a new family of precious metal‐free robust dye‐sensitized photoelectrodes for water oxidation, in which a variety of common organic chromophores can be employed in conjunction with CoFe PB structures.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.