The interplay between spin states, geometries and biological activity of Fe(III) and Mn(II) complexes with thiosemicarbazone

Fe(III) and Mn(II) complexes with condensation product of thiosemicarbazide and 2-acetylthiazole (HL1, (E)-2-(1-(thiazol-2-yl)ethylidene)hydrazine-1-carbothioamide) have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. In both complexes, the thiosemicarbazone ligand is coordinated in deprotonated form through the NNS donor set of atoms. However, while Fe(III) complex is in the doublet ground state with distorted octahedral geometry, the coordination environment around Mn(II) is distorted trigonal-prismatic, and the sextet state is found to be the ground state. DFT calculations were performed to rationalize spin state preferences, and continuous shape measure describes the deviation from ideal six-coordinated polyhedral geometries in the ground and excited states. Antimicrobial activity (against a panel of Gram-negative and Gram-positive bacteria, two yeast, and one fungal strain), brine shrimp assay, and DPPH radical scavenging activity of both complexes were evaluated, and these results relate to the electronic structure of the complexes

Synthesis, characterization, antimicrobial and cytotoxic activity and DNA-binding properties of d-metal complexes with hydrazones of Girard’s T and P reagents

Abstract: In this work synthesis, characterization and crystal structures of 1, Zn(II) complex ([ZnL1(NCS)2]), with (E)-1-(2-oxo-2-(2-(quinolin-2-ylmethylene)hydrazinyl)ethyl)pyridin-1-ium chloride (HL1Cl) and 2, Bi(III) complex ([BiHL2Cl4] × 1/2CH3OH), with (E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(thiazol-2-yl)ethylidene)hydrazinyl)ethan-1-aminium chloride (HL2Cl), have been reported. Zn(II) complex possesses a distorted trigonal bipyramidal geometry while surroundings around Bi(III) ion are extended pentagonal bipyramidal. Antimicrobial activity, brine shrimp assay and DPPH radical scavenging activity of both complexes, including previously synthesized complexes with HL2Cl ligand (Zn(II) and Ni(II)) and complexes with (E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethan-1-aminium chloride (HL3Cl) (Zn(II), Cu(II), Cd(II), Co(II), Fe(III), Ni(II)), were evaluated. For the most active complexes, cytotoxic activity against five malignant cancer cell lines (HeLa, A375, MCF7, PC-3 and A549) and normal cell line HaCaT, as well as generation of reactive oxygen species (ROS), was tested. Graphic abstract: [Figure not available: see fulltext.

Developmental dysplasia of the hip in cerebral palsy–surgical treatment

Developmental dysplasia of the hip (DDH) in cerebral palsy (CP) is very rare, and very little clinical data is available. We have analysed the results of open reduction of the hip (Howorth), acetabuloplasty (Salter, Pemberton), pelvic osteotomy (Chiari) and femoral osteotomy in the treatment of the DDH in CP patients. Radiographic assessment was based on the Severin grading classification system and measurements of migration percentage (MP) before and after surgery. Clinical results were analysed using the Ponsetti classification system in ambulatory patients. A total of 45 hips in 31 patients were treated surgically. The average age of the patients was 5.2 years (range: 2–16 years). The average follow-up was 9.6 years (range: 3–28 years). Analysis of the radiographic results according to Severin placed 35 hips (77.8%) in groups 1 and 2 and ten hips (22.2%) in groups 3 and higher. The average preoperative MP value was 78.7% and the average postoperative MP was 15.2%. Redislocation occurred in three hips. Clinical results were disappointing: based on Ponsetti assessment 14 hips (36.8%) were classified in the first three groups and 24 hips (63.2%) in the last three groups. This analysis suggests that these surgical procedures could be applied in treating DDH in CP