Synthesis,characterization, crystal structure determination and computational study of the high-spin iron(II) 2-cyanopyrazine complex trans-[Fe(pzCN)4Cl2]

A new mononuclear high-spin complex, trans-[Fe(pzCN)₄Cl₂] (1), was prepared from the reaction of FeCl₂.4H₂O and 2-cyanopyrazine (pzCN) in acetonitrile as a solvent. Suitable crystals of this complex for crystal structure determination were collected by slow evaporation of the produced pale orange solution. Complex 1 was characterized by elemental analysis (CHN), spectral methods (IR and UV–Vis), and single-crystal X-ray diffraction. The X-ray structural analysis indicated that the iron(II) is six-coordinated in an octahedral configuration by four N atoms from four 2-cyanopyrazine ligands and two chloride anions. Furthermore, the average of Fe–N bond lengths is 2.284(1)Å. It is well known that in the high-spin iron(II) phenanthroline and bipyridine complexes, the Fe–N bond lengths are around 2.2 Å. So, due to the Fe–N bond length in this complex, the iron(II) is unambiguously high-spin. The experimental evaluations on 1 have been complemented theoretically by the density functional theory (DFT) and TD-DFT calculations. The character of the Fe–N and Fe–Cl bonds was investigated using quantum theory of atoms in molecules. Additionally, electron delocalization and hyper-conjugative interactions of the synthesized complex were evaluated by natural bond orbital calculations.

     

Development of DNA-Designed Avian IgY Antibodies for Detection of Mycobacterium avium subsp. paratuberculosis Heat Shock Protein 70 (Hsp70) and Anti-Hsp70 Antibodies in the Serum of Normal Cattle

Mycobacterium avium subsp. paratuberculosis heat shock protein 70 (MAPHsp70) is an immunodominant antigen, which can be used as a subunit vaccine against bovine paratuberculosis. In the present study, we evaluated the immunogenic activities of MAPHsp70 expressed by DNA vaccine in chicken and the use of prepared specific avian IgY antibodies for western blotting and ELISA methods. The gene encoding MAP Hsp70 was subcloned into the eukaryotic expression vector, pcDNA3.1, and the recombinant plasmid (pcDNA3.1-MAP Hsp70) transfected into COS-7 cells. Chickens were also immunized with pcDNA3.1-MAP Hsp70, and egg yolk antibodies extracted from eggs were collected after immunization. DNA-designed IgY antibody was used in Western blotting analysis to detect the expression of MAPHsp70, and in a sandwich ELISA to assess the prevalence of anti-MAPHsp70 antibodies in cattle serum. Western blotting results indicate the expression of rMAP hsp70 in COS-7 cells and sandwich ELISA could detect anti-MAPHsp70 antibodies in 7.5% of cows. Chicken immunization with pcDNA3.1-MAPHsp70 could demonstrate the effective production of anti-MAPHsp70 IgY antibodies. Monospecific anti-MAPHsp70 antibody generated in chickens is useful for detection of MAPHsp70 peptide in cell culture and MAP lysate.     

Synthesis,spectroscopic characterization,crystal structure determination and DFT calculations of [Au(Me<Subscript>2</Subscript>phen)Br<Subscript>2</Subscript>][AuBr<Subscript>2</Subscript>]

New mixed valence gold(III/I) salt containing two complexes [Au(Me₂phen)Br₂][AuBr₂] (1) was prepared from the reaction of AuBr₃ and 5,6-dimethyl-1,10-phenanthroline (Me₂phen) in a mixture of methanol and acetonitrile. Suitable crystals of 1 for X-ray diffraction measurement were obtained by slow evaporation of the resulted red solution at room temperature. This complex was characterized by spectral methods (IR, UV–Vis and ¹H NMR), elemental analysis and single-crystal X-ray diffraction. The X-ray structural analysis indicated that the asymmetric unit of 1 contains one [Au(Me₂phen)Br₂]⁺ cation and two half anions of [AuBr₂]^ˉ. Furthermore, the packing diagram of this complex, 3-D structure stabilized by intermolecular Au…Br and Au…π interactions and intermolecular C–H···Br hydrogen bonds. The experimental investigations on complex have been accompanied computationally by the density functional theory (DFT) and time-dependent DFT calculations. The nature of the Au–N bonds was investigated using quantum theory of atoms in molecules. Moreover, natural bond orbital analysis carried out to obtain hyper-conjugative interactions and electron delocalization on the complex.