A series of sterically shielded pyrrolidine nitroxides were synthesized and their reduction by ascorbate (vitamin C) indicate that nitroxide 3 – a tetraethyl derivative of 3-carboxy-PROXYL – is reduced at the slowest rate among known nitroxides, i.e., at a 60-fold slower rate than that for 3-carboxy-PROXYL.
The merging of photoredox
trifluoromethylation with hybrid P450
BM3 variants has enabled the selective light-driven functionalization
of several arenes. This approach capitalizes on the unique photochemical
properties of the Ru(II)-diimine photosensitizer to initiate single
electron transfer events. Under photoredox conditions, a CF3 radical promoted by the d6 metal complex can add to arenes.
In the hybrid P450 BM3 enzymes, the covalently attached Ru(II)-diimine
photosensitizer provides the necessary electrons to perform, upon
visible light activation, P450 oxyfunctionalizations on the trifluoromethylated
substrates.
Protein dimerization often occurs in many biological systems as to provide structural and functional advantages. A tris(5‐iodoacetamido‐1,10‐phenanthroline)Ruthenium(II) complex was shown to promote the covalent dimerization of a P450 BM3 heme domain mutant containing a surface‐exposed nonnative single cysteine residue. The formation of homodimeric species was confirmed by protein gel electrophoresis, mass spectrometry and UV–Vis spectroscopy. The dimeric species could be separated from the monomer and aggregates by size‐exclusion chromatography. Docking simulation reveals a plausible structure with two proteins covalently conjugated to the inorganic compound.
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