The gold(I) complexes of the general formula [Au(L(n))(PPh(3))]·xH(2)O (1-8; n = 1-8 and x = 0-1.5), where L(n) stands for a deprotonated form of the benzyl-substituted derivatives of 6-benzylaminopurine, were prepared, thoroughly characterized (elemental analyses, FT-IR, Raman and multinuclear NMR spectroscopy, ESI+ mass spectrometry, conductivity, DFT calculations), and studied for their in vitro cytotoxicity and in vitro and in vivo anti-inflammatory effects on LPS-activated macrophages (derived from THP-1 cell line) and using the carrageenan-induced hind paw edema model on rats. The obtained results indicate that the representative complexes (1, 3, 6) exhibit a strong ability to reduce the production of pro-inflammatory cytokines TNF-α, IL-1β and HMGB1 without influence on the secretion of anti-inflammatory cytokine IL-1RA in the LPS-activated macrophages. The complexes also significantly influence the formation of edema, caused by the intraplantar application of polysaccharide λ-carrageenan to rats in vivo. All the tested complexes showed similar or better biological effects as compared with Auranofin, but contrary to Auranofin they were found to be less cytotoxic in vitro. The obtained results clearly indicate that the gold(I) complexes behave as very effective anti-inflammatory agents and could prove to be useful for the treatment of difficult to treat inflammatory diseases such as rheumatoid arthritis.
A thorough study of structural and magnetic properties was performed on a series of trinuclear and dinuclear Mn(III)/Fe(III) complexes consisting of [M(L4)(Solv)](+) and [Fe(CN)5(NO)](2-) moieties (M = Fe(III) or Mn(III), Solv = H2O or CH3OH, L4 = tetradentate salen-type ligands), in which dominant magnetic exchange is mediated by O(S)-H···O(Ph) hydrogen bonds in [M(L4)(Solv)](+)···[M(L4)(Solv)](+) supramolecular dimers. As deduced from magnetic analysis involving the determination of zero-field splitting (ZFS) parameters for Mn(III) and Fe(III) ions, as well as from comprehensive DFT calculations and modelling, it may be concluded that the strength of the magnetic exchange is correlated with the number of hydrogen bonds and with the O(Ph)···O(S) distance between the phenolic oxygen atom of the salen-type ligand (O(Ph)) and the oxygen atom of the solvent molecule coordinated to the adjacent metal atom (O(S)).
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