Instantaneous, stoichiometric generation of powerfully reducing states of protein active sites using Eu(II) and polyaminocarboxylate ligands

Addition of an equivalent of a polyaminocarboxylate ligand (L) to a solution of a redox protein and the aqua Eu2+ ion results in the instantaneous in situ generation of a very powerful reductant Eu(II)-L that can rapidly drive an electron stoichiometrically onto a redox centre having an extremely negative reduction potential (lower than -1 V): this is exemplified by straightforward generation of the super-reduced state of the Fe-protein of nitrogenase.     

The Berezin transform and radial operators

We analyze the connection between compactness of operators on the Bergman space and the boundary behaviour of the corresponding Berezin transform. We prove that for a special class of operators that we call radial operators, an oscilation criterion is a sufficient condition under which the compactness of an operator is equivalent to the vanishing of the Berezin transform on the unit circle. We further study a special class of radial operators, i.e., Toeplitz operators with a radial symbol.

     

A New Approach to Chalcogen–Nitrogen π-Heterocyclic Radicals

This paper gives a brief overview of a new approach to chalcogen–nitrogen heterocyclic π-radicals, particularly 1,2,3- and 1,3,2-benzodithiazolyls, based on thermolysis or photolysis of closed-shell precursors (such as 1,3,2,4-benzodithiadiazines and their 1-Se congeners, 1,2,4,3,5- and 1,3,5,2,4-benzotrithiadiazepines, and some other sulfur–nitrogen rings and cages). The approach allows obtaining radicals hardly accessible or inaccessible in other ways, especially, fluorinated radicals. The identity of radicals prepared is confirmed by electron paramagnetic resonance spectroscopy in combination with density functional theory calculations.