Radical -Adenosyl-l-Methionine Enzyme PylB: A C-Centered Radical to Convert l-Lysine into (3)-3-Methyl-d-Ornithine.

PylB is a radical -adenosyl-l-methionine (SAM) enzyme predicted to convert l-lysine into (3)-3-methyl-d-ornithine, a precursor in the biosynthesis of the 22nd proteogenic amino acid pyrrolysine. This protein highly resembles that of the radical SAM tyrosine and tryptophan lyases, which activate their substrate by abstracting a H atom from the amino-nitrogen position. Here, combining assays, analytical methods, electron paramagnetic resonance spectroscopy, and theoretical methods, we demonstrated that instead, PylB activates its substrate by abstracting a H atom from the Cγ position of l-lysine to afford the radical-based β-scission.

Mechanistic Insight into the Photocontrolled Cationic Polymerization of Vinyl Ethers.

The mechanism of the recently reported photocontrolled cationic polymerization of vinyl ethers was investigated using a variety of catalysts and chain-transfer agents (CTAs) as well as diverse spectroscopic and electrochemical analytical techniques. Our study revealed a complex activation step characterized by one-electron oxidation of the CTA. This oxidation is followed by mesolytic cleavage of the resulting radical cation species, which leads to the generation of a reactive cation-this species initiates the polymerization of the vinyl ether monomer-and a dithiocarbamate radical that is likely in equilibrium with the corresponding thiuram disulfide dimer.

High-Spin Polymers: Ferromagnetic Coupling of S = 1 Hexaazacyclophane Units up to a Pure S = 2 Polycyclophane.

Triarylamines oxidized to radical cations can be used as stable spins sources for the design of high-spin compounds. Here, we present the synthesis of the polyarylamine-containing hexaazacyclophanes linked via meta-terphenyl bridges. Spins, created after oxidation of the polymer, can be coupled magnetically in cyclophane moieties via meta-phenyl and along the polymer chain via meta-terphenyl units.