Tadeusz Muzioł

Synthesis, characterization and antitumor properties of two highly cytotoxic ruthenium(III) complexes with bulky triazolopyrimidine ligands

Two ruthenium(III) complexes composed of 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine (dbtp) ligands were prepared and structurally characterized by X-ray crystallography, IR, UV-Vis, EPR spectroscopies and cyclic voltammetry (CV). The crystal structures of trans-[RuCl(3)(H(2)O)(dbtp)(2)] 1 and mer-[RuCl(3)(dbtp)(3)]·0.815OCMe(2) 2 showed slightly distorted octahedral geometries with two 1 or three 2 monodentate dbtp ligands bound in a head-to-head orientation. In both complexes, the heterocyclic dbtp ligands were bound to the ruthenium(III) ion through the N3 nitrogen atom. A cytotoxicity assay of both ruthenium(III) compounds against two human cell lines (A549 - non-small cell lung carcinoma and T47D - breast carcinoma) was performed. The ruthenium(III) complexes showed excellent cytotoxicity with IC(50) values in the range of 0.02-2.4 μM against both cancer cell lines. In addition, the in vitro cytotoxic values of the ruthenium(III) compounds were 35-times for 1 and 172-times for 2 higher against T47D than the clinically used antitumor drug cisplatin.

New procedure of selected biogenic amines determination in wine samples by HPLC

A new procedure for determination of biogenic amines (BA): histamine, phenethylamine, tyramine and tryptamine, based on the derivatization reaction with 2-chloro-1,3-dinitro-5-(trifluoromethyl)-benzene (CNBF), is proposed. The amines derivatives with CNBF were isolated and characterized by X-ray crystallography and (1)H, (13)C, (19)F NMR spectroscopy in solution. The novelty of the procedure is based on the pure and well-characterized products of the amines derivatization reaction. The method was applied for the simultaneous analysis of the above mentioned biogenic amines in wine samples by the reversed phase-high performance liquid chromatography. The procedure revealed correlation coefficients (R(2)) between 0.9997 and 0.9999, and linear range: 0.10-9.00 mg L(-1) (histamine); 0.10-9.36 mg L(-1) (tyramine); 0.09-8.64 mg L(-1) (tryptamine) and 0.10-8.64 mg L(-1) (phenethylamine), whereas accuracy was 97%-102% (recovery test). Detection limit of biogenic amines in wine samples was 0.02-0.03 mg L(-1), whereas quantification limit ranged 0.05-0.10 mg L(-1). The variation coefficients for the analyzed amines ranged between 0.49% and 3.92%. Obtained BA derivatives enhanced separation the analytes on chromatograms due to the inhibition of hydrolysis reaction and the reduction of by-products formation.

The molecular structures of copper(II) chloroacetate complexes with5,7-dimethyl-1,2,4-triazolo-[1,5-α]-pyrimidine and 5,7-diphenyl-1,2,4-triazolo-[1,5-α]-pyrimidine

Abstract Copper(II) complexes of formula Cu2(CH2ClCOO)4(dmtp)2 (1) and Cu2(CN2ClCOO)4(dptp)2 (2), wheredmtp=5,7-dimethyl-1,2,4-triazolo-[1,5-α]-pyrimidine anddptp=5,7-diphenyl-1,2,4-triazolo-[1,5-α]-pyrimidine, were obtained. The X-ray diffraction analysis of 1 exhibited the dimeric structure with chloroacetate bridges. The coordination sphere of Cu(II) ion is a slightly distorted square pyramid, with 4 equatorial carboxylic oxygens and anaxially N(3) bonded dmtp molecule. The distance Cu–Cu is 2.7035(7) Aand the distance between Cu and O4 plane is 0.239(1) A(towards the axial ligand). The distances Cu–O are 1.954(2)–1.981(2) A,Cu–N 2.150(1) A. The angles O–Cu–O are 87.88(8)–90.56(8)° and166.04(6)–166.07(5)°, O–Cu–N 90.08(7)–103.76(7)°. The O4 plane is not perpendicular to the Cu · · · Cu line, the angles O–Cu–Cu being 82.04(5)–84.00(5)° and N–Cu–Cu169.54(4)°. Spectroscopic (IR, UV, EPR) and magnetic studies suggested that 2 has the analogous structure to 1.

Co(II), Ni(II) and Cu(II) complexes with phenylthiazole and thiosemicarbazone-derived ligands: synthesis, structure and cytotoxic effects

Complexes of Co(II), Ni(II) and Cu(II) with 2-(3,5-dimethyl-1H-pyrazole-1-yl)-4-phenyl-1,3-thiazole (a) and 3,5-dimethyl-1H-pyrazole-1-carbothioamide (b) ligands were synthesized. The crystal and molecular structures of four of them were determined by the X-ray diffraction method. In the complexes with ligand a the metal atom was bound via two nitrogen atoms, whereas ligand b interacted through the nitrogen and sulfur atoms. Comparing the coordination modes observed for both studied ligands, the thiocarbamoyl sulfur atom can participate in metal binding and in bridge formation, whereas the thiazole (aromatic) sulfur atom is not involved in the coordination. This effect seems to enhance (at least partially) conformational flexibility. Hydrogen bonds played a principal role in the crystal network formation of the analyzed compounds. The cytotoxic activity of the complexes against HL-60 and NALM-6 leukemia cells and the WM-115 melanoma cell line was also measured. The copper(II) complex with the thiosemicarbazone ligand (7b) exhibited relatively high cytotoxicity towards all tested tumor cells. The cytotoxicity of copper(II) complexes 7b and 9b against the melanoma WM-115 cells was over three times higher than that of cisplatin.

Synthesis and detailed characterization of cis-dichloridobispicolinatoruthenate(III) as solid and in solution

Abstract Three water-soluble ruthenium(III) compounds, Y[cis-RuCl2(pic)2]⋅nH2O (where pic = picolinate anion, Y = H(Hpic)2+ (1), H2pic+ (2) or K+ (3), n = 2, 1.5, and 2.5, respectively), were synthesized and their X-ray structures determined. Compound 1 was fully characterized both as solid and in aqueous solution by elemental analysis, magnetic susceptibility measurements, EPR, IR and UV-visible spectroscopy, cyclic voltammetry, microwave plasma atomic emission, and mass spectrometry, capillary electrophoresis and chromatographic methods. It was shown that the coordination geometry around the low spin (S = ½) RuIII center is distorted octahedral with the chlorido ligands in a cis configuration. Furthermore, all the measurements showed that the structures in the solid state and solution are absolutely identical with the cis-[RuCl2(pic)2]− anion being inert in aqueous solution. Microbial studies showed that 1 exerts a strong inhibition on the growth and increased mortality level of the bacterial strains – Escherichia coli, Pseudomonas sp., Sarcina sp., Micrococcus sp., Serratia sp., Bacillus cereus, Bacillus subtilis and yeast – Saccharomyces cerevisiae.

Structural and thermal characterization of copper(II) complexes with phenyl-2-pyridylketoxime and deposition of thin films by spin coating

Four copper(II) oxime complexes, [Cu(HPPK)(PPK)X] (HPPK = phenyl-2-pyridylketoxime and X = CI− (I), CF3COO− (II), C3F7COO− (III), and [Cu(PPK)2]2 (IV)), were synthesized and characterized by elemental analysis, infrared spectroscopy (IR), and single-crystal X-ray diffraction (XRD). XRD analysis revealed that I–III contain copper(II) coordinated by four nitrogen atoms from two oxime molecules in the basal plane and one monodentate anion X in the apical position of a distorted square pyramid. Complex IV is dimeric and it is formed by two Cu(PPK)2 units. Bridges between these units are formed by the two oxygen atoms of the deprotonated oxime groups. Thermal stability of I–IV was investigated by thermogravimetric analysis (TGA) in air and in nitrogen atmosphere, respectively. Evolved gaseous decomposition products were characterized by IR. I–IV decompose via multistep processes. Fluorocarbons and CO2 were observed to be the most abundant gaseous species evolved. Preliminary ammonolysis experiments were performed to examine the possibility of using II and IV as precursors for the synthesis of copper nitride. Moreover, solutions of IV were spin-coated onto silicon substrates. Surface structure and morphology of the resulting films were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM) and layers with island-like distribution of material were observed.