Photoactivation Properties of Self-n-Doped Perylene Diimides: Concentration-dependent Radical Anion and Dianion Formation.

Perylene diimides (PDIs) have garnered attention as organic photocatalysts in recent years for their ability to drive challenging synthetic transformations, such as aryl halide reduction and olefin iodoperfluoroalkylation. Previous work in this area employs spectator pendant groups attached to the imide nitrogen positions of PDIs that are only added to impart solubility. In this work, we employ electron-rich ammonium iodide or ammonium hydroxide pendant groups capable of self-n-doping the PDI core to form radical anions ( ) and dianions ( ).

Selectively Altering the Reactivity of Transient Organic Radical Ions via Their Solvation Environment.

Photoexcitation of the charge transfer band of electron donor-acceptor complexes composed of toluene and 1,2,4,5-tetracyanobenzene yields organic radical ion pairs whose ultrafast reactive dynamics are determined by equilibrium solvent properties. A comparative study of ultrafast reaction rates in a series of alkane alcohols identified their dependence on the local polarizability and hydrogen bond donating/accepting character of the solvent. Because of the rapid and efficient equilibration of these radical ion pairs into solvent-separated species, simple modifications to bulk conditions can be used as a means to selectively alter their decay rates.

Loquacious-PD regulates the terminus-dependent molecular recognition of Dicer-2 toward double-stranded RNA.

Dicer-2 cleaves double-stranded RNA into siRNAs in a terminus-dependent manner as part of 's RNA interference pathway. Using ultrafast fluorescence, we probe the local environment of chromophores at the dsRNA terminus upon binding by Dicer-2 and interrogate the effects of Loquacious-PD, an accessory protein. We find substrate-selective modes of molecular recognition that distinguish between blunt and 3'overhang termini, but whose differences are greatly reduced by Loquacious-PD.

Transient kinetic studies of the antiviral Dicer-2 reveal roles of ATP in self-nonself discrimination.

Some RIG-I-like receptors (RLRs) discriminate viral and cellular dsRNA by their termini, and Dicer-2 (dmDcr-2) differentially processes dsRNA with blunt or 2 nucleotide 3'-overhanging termini. We investigated the transient kinetic mechanism of the dmDcr-2 reaction using a rapid reaction stopped-flow technique and time-resolved fluorescence spectroscopy. Indeed, we found that ATP binding to dmDcr-2's helicase domain impacts association and dissociation kinetics of dsRNA in a termini-dependent manner, revealing termini-dependent discrimination of dsRNA on a biologically relevant time scale (seconds).

Role of Polar Protic Solvents in the Dissociation and Reactivity of Photogenerated Radical Ion Pairs.

The UV photolysis of bimolecular charge transfer complexes is employed to yield reactive radical ions in their solvent-equilibrated electronic ground state. In polar protic media, noncovalent complexes of 1,2,4,5-tetracyanobenzene and toluene undergo efficient, ultrafast dissociation to ion pairs and equilibrate with their solvent environment before the resulting radical ions engage in electron transfer and proton abstraction on subnanosecond time scales. Solvent molecules play a critical role in these reactive pathways and in the dissociation and relaxation processes that precede them.