Chemoselective Proteomics, Zinc Fingers, and a Zinc(II) Model for H2S Mediated Persulfidation.

The gasotransmitter hydrogen sulfide (H2S) is thought to be involved in the post-translational modification of cysteine residues to produce reactive persulfides. A persulfide-specific chemoselective proteomics approach with mammalian cells has identified a broad range of zinc finger (ZF) proteins as targets of persulfidation. Parallel studies with isolated ZFs show that persulfidation is mediated by ZnII, O2, and H2S, with intermediates involving oxygen- and sulfur-based radicals detected by mass spectrometry and optical spectroscopies. A small molecule ZnII complex exhibits analogous reactivity with H2S and O2, giving a persulfidated product. These data show that ZnII is not just a biological structural element, but also plays a critical role in mediating H2S-dependent persulfidation. ZF persulfidation appears to be a general post-translational modification and a possible conduit for H2S signaling. This work has implications for our understanding of H2S-mediated signaling and the regulation of ZFs in cellular physiology and development.

Geometrical variations of two manganese(II) complexes with closely related quinoline-based tripodal ligands.

Structural analyses of the compounds di-µ-acetato-κ4 O:O'-bis-{[2-meth-oxy-N,N-bis-(quinolin-2-ylmeth-yl)ethanamine-κ4 N,N',N'',O]manganese(II)} bis-(tetra-phen-yl-borate) di-chloro-methane 1.45-solvate, [Mn2(C23O2)2(C23H23N3O)2](C24H20B)·1.45CH2Cl2 or [Mn(DQMEA)(µ-OAc)2Mn(DQMEA)](BPh4)2·1.45CH2Cl2 or [1](BPh4)2·1.45CH2Cl2, and (acetato-κO)[2-hy-droxy-N,N-bis(quinolin-2-ylmeth-yl)ethanamine-κ4 N,N',N'',O](methanol-κO)manganese(II) tetra-phenyl-borate methanol monosolvate, [Mn(CH3COO)(C22H21N3O)(CH3OH)](C24H20B)·CH3OH or [Mn(DQEA)(OAc)(CH3OH)]BPh4·CH3OH or [2]BPh4·CH3OH, by single-crystal X-ray diffraction reveal distinct differences in the geometry of coordination of the tripodal DQEA and DQMEA ligands to MnII ions. In the asymmetric unit, compound [1](BPh4)2·(CH2Cl2)1.45 crystallizes as a dimer in which each manganese(II) center is coordinated by the central amine nitro-gen, the nitro-gen atom of each quinoline group, and the meth-oxy-oxygen of the tetra-dentate DQMEA ligand, and two bridging-acetate oxygen atoms. The symmetric MnII centers have a distorted, octa-hedral geometry in which the quinoline nitro-gen atoms are trans to each other resulting in co-planarity of the quinoline rings. For each MnII center, a coordinated acetate oxygen participates in C-H⋯O hydrogen-bonding inter-actions with the two quinolyl moieties, further stabilizing the trans structure. Within the crystal, weak π-π stacking inter-actions and inter-molecular cation-anion inter-actions stabilize the crystal packing. In the asymmetric unit, compound [2]BPh4·CH3OH crystallizes as a monomer in which the manganese(II) ion is coordinated to the central nitro-gen, the nitro-gen atom of each quinoline group, and the alcohol oxygen of the tetra-dentate DQEA ligand, an oxygen atom of OAc, and the oxygen atom of a methanol ligand. The geometry of the MnII center in [2]BPh4·CH3OH is also a distorted octa-hedron, but the quinoline nitro-gen atoms are cis to each other in this structure. Hydrogen bonding between the acetate oxygen atoms and hydroxyl (O-H⋯O) and quinolyl (C-H⋯O and N-H⋯O) moieties of the DQEA ligand stabilize the complex in this cis configuration. Within the crystal, dimerization of complexes occurs by the formation of a pair of inter-molecular O3-H3⋯O2 hydrogen bonds between the coordinated hydroxyl oxygen of the DQEA ligand of one complex and an acetate oxygen of another. Additional hydrogen-bonding and inter-molecular cation-anion inter-actions contribute to the crystal packing.