Zinc(II)-methimazole complexes: synthesis and reactivity

The tetrahedral S-coordinated complex [Zn(MeImHS)(4)](ClO4)(2), synthesised from the reaction of [Zn(ClO4)(2)] with methimazole (1-methyl-3H-imidazole-2-thione, MeImHS), reacts with triethylamine to yield the homoleptic complex [Zn(MeImS)(2)] (MeImS = anion methimazole). ESI-MS and MAS C-13-NMR experiments supported MeImS acting as a (N, S)-chelating ligand. The DFT-optimised structure of [Zn(MeImS)(2)] is also reported and the main bond lengths compared to those of related Zn-methimazole complexes. The complex [Zn(MeImS)(2)] reacts under mild conditions with methyl iodide and separates the novel complex [Zn(MeImSMe)(2)I-2] (MeImSMe = S-methylmethimazole). X-ray diffraction analysis of the complex shows a ZnI2N2 core, with the methyl thioethers uncoordinated to zinc. Conversely, the reaction of [Zn( MeImS)(2)] with hydroiodic acid led to the formation of the complex [Zn(MeImHS)(2)I-2] having a ZnI2S2 core with the neutral methimazole units S-coordinating the metal centre. The Zn-coordinated methimazole can markedly modify the coordination environment when changing from its thione to thionate form and vice versa. The study of the interaction of the drug methimazole with the complex [Zn(MeIm)(4)](2+) (MeIm = 1-methylimidazole) - as a model for Zn-enzymes containing a N-4 donor set from histidine residues shows that methimazole displaces only one of the coordinated MeIm molecules; the formation constant of the mixed complex [Zn(MeIm)(3)(MeImHS)](2+) was determined

Activation of Vitamin D3 in Bovine Mastitis Caused by Streptococcus uberis

Inflamed mammary tissue of three cows infected with Streptococcus uberis was found to have higher concentrations of 1α-hydroxylase than un-inflamed control mammary glands. Increased levels of 1α−hydroxylase resulted in increased production of 1,25-dihydroxyvitamin D3. Therefore, vitamin D3 may have a role in the inflammation and resolution of bovine mastitis

1,25-Dihydroxyvitamin D3 Enhances Bovine Mammary Epithelial Innate Immune Responses

Bovine mammary epithelial cells that were treated with bacterial lipopolysaccharide and 1,25-dihydroxyvitamin D3 showed an increase in the expression of the genes for inducible nitric oxide synthase (iNOS) and S100 calcium binding protein A12 (S100 A12). iNOS and S100 A12 are part of the innate immune response and expressed in the mammary gland during mastitis. Production of 1,25- dihydroxyvitamin D3 in the mammary gland during mastitis, then, may be an important component of the innate immune response

Regulation of Immune Responses to Mycobacteria bovis by a Paracrine Mechanism of Vitamin D Signaling in Cattle

We provide evidence that T-cell responses to Mycobacteria bovis are suppressed by the production of 1,25-dihydroxyvitamin D3 in monocytes and B-cells from cattle. Current vitamin D requirements for cattle are solely based on the classical endocrine mechanism of vitamin D signaling that regulates calcium homeostasis and should be re-evaluated to account for vitamin D signaling mechanisms in the immune system

A structural spproach to the strength evaluation of linear chalcogen bonds

The experimental structural features of chalcogen bonding (ChB) interactions in over 34,000 linear fragments R–Ch⋯A (Ch = S, Se, Te; R = C, N, O, S, Se, Te; A = N, O, S, Se, Te, F, Cl, Br, I) were analyzed. The bond distances dR–Ch and the interaction distances dCh⋯A were investigated, and the functions δR–Ch and δCh⋯A were introduced to compare the structural data of R–Ch⋯A fragments involving different Ch atoms. The functions δR−Ch and δCh⋯A were calculated by normalizing the differences between the relevant bond dR–Ch and ChB interaction dCh⋯A distances with respect to the sum of the relevant covalent (rcovR + rcovCh) and the van der Waals (vdW) radii (rvdWCh + rvdWA), respectively. A systematic comparison is presented, highlighting the role of the chalcogen involved, the role of the R atoms covalently bonded to the Ch, and the role of the A species playing the role of chalcogen bond acceptor. Based on the results obtained, an innovative approach is proposed for the evaluation and categorization of the ChB strength based on structural data

Reactivity of the drug methimazole and its iodine adduct with elemental zinc

The reactivity of zinc complexes with N,S-donor molecules may be of relevance to the study of Zn-metalloproteins and -metalloenzymes. In this context, the zinc complex [Zn(MeImSH)2I2] was synthesised by the reaction of zinc powder with the 1 : 1 iodine adduct of the drug methimazole [(MeImSH)·I2]. The molecular structure of the complex, elucidated by X-ray diffraction analysis, showed a tetrahedral zinc(II) centre coordinated by two neutral methimazole units (through the sulfur atoms) and two iodides. From the reaction of MeImSH and Zn powder, the complex [Zn(MeImSH)(MeImS)2] (MeImS = deprotonated form of methimazole) was separated and characterised. An analysis of the crystal packing of the neutral complexes [Zn(MeImSH)2X2] (X = I, Br and Cl) and the ionic complex [Zn(MeImSH)3I]I showed that in all of the complexes the sulfur atom, in addition to binding to the metal centre, contributes to the formation of 1-D chains built via C(4)–HS and N–HX interactions in the neutral complexes, and via C(4)–HS and N–CH3S interactions in the ionic complex [Zn(MeImSH)3I]I. The deprotonation/protonation of the coordinated methimazole units can modulate the coordination environment at the Zn core. From the reaction of complex [Zn(MeImSH)3I]I with a strong non-coordinating organic base, we have shown that, as a consequence of the NH deprotonation of methimazole S-coordinated to zinc(II), the ligand coordination mode changes from S-monodentate to N,S-bridging. Correspondingly, in the complex [Zn(MeImSH)(MeImS)2], the MeImS that displays the N,S-bridging mode at zinc can be N-protonated and thereby changes to the S-monodentate coordination

Photographic detection of Cadmium(II) and Zinc(II) ions

The binding properties of two 2,8-dithia-5-aza-2,6-pyridinophane-based ligands, bearing respectively coumarin (HNCum) and naphthol-benzoxaazole (HNBO) optically active units as pendant arms, were studied with the aim of transition metal cations selective detection. The novel all-solid-state optodes were obtained by inclusion of fluorophores inside PVC-based polymeric films. The influence of lipophilic sites incorporation and plasticizer nature on pyridinophane-based optodes response was investigated. An enhanced selectivity of the ligands towards Cadmium(II) and Zinc(II) ions was detected. Light Emitting Diode, LED 380 nm, was used as light source, and a digital camera as a signal detector. The results obtained demonstrated the suitability of the developed optodes to perform fast and low cost simultaneous monitoring of Zn2+and Cd2+ ions by means of familiar devices and chemometrics. © 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license

Aza- and Mixed Thia/Aza-Macrocyclic Receptors with Quinoline-Bearing Pendant Arms for Optical Discrimination of Zinc(II) or Cadmium(II) Ions

The synthesis and coordination properties of two fluorescent chemosensors, featuring [9]aneN3 (1,4,7-triazacyclononane; L1) and [12]aneNS3 (1-aza-4,7,10-trithiacyclododecane; L2) as receptor units, and a quinoline pendant arm with an amide group as a functional group spacer are described. The optical responses of L1 and L2 in the presence of several metal ions were analysed in MeCN/H2O (1 : 4 v/v) solutions. A selective chelation enhancement of fluorescence (CHEF) effect was observed in the presence of Zn2+ in the case of L1, and in the presence of Cd2+ in the case of L2, following the formation of a 1 : 1 and a 1 : 2 metal/ligand complex, respectively, which was also confirmed by potentiometric measurements. 1H and 13C NMR measurements in CD3CN/CDCl3 in combination with molecular mechanics calculations show that for both complexes of L1 and L2 with Zn2+ and Cd2+, respectively, the coordination of the carbonyl group from the pendant arm could be the origin of the observed optical selectivity

Functionalization and Coordination Effects on the Structural Chemistry of Pendant Arm Derivatives of 1,4,7-trithia-10-aza-cyclododecane ([12]aneNS3)

The effect of different pendant arms on the structural chemistry of the 1,4,7-trithia-10-aza-cyclododecane ([12]aneNS3) macrocycle is discussed in relation to the coordination chemistry of all known functionalized derivatives of [12]aneNS3, which have been structurally characterized