Aleksander Kufelnicki

Synthesis, X-ray structure and cytotoxic effect of nickel(II) complexes with pyrazole ligands.

Here we present the synthesis of the new Ni(II) complexes with chelating ligands 1-benzothiazol-2-yl-3,5-dimethyl-1H-pyrazole (a), 5-(2-hydroxyphenyl)-3-methyl-1-(2-pyridylo)-1H-pyrazole-4-carboxylic acid methyl ester (b) and 1-benzothiazol-2-yl-5-(2-hydroxyphenyl)-3-methyl-1H-pyrazole-4-carboxylic acid methyl ester (c). These ligands a-c create solid complexes with Ni(II). The crystal and molecular structures of two complexes were determined by X-ray diffraction method. Thermal stability of two complexes with ligand c by TG/DTG and DSC methods were also shown. Cytotoxic activity of all the complexes against three tumour cell lines and to normal endothelial cells (HUVEC) was also estimated. Complexes with ligand c exhibited relatively high cytotoxic activity towards HL-60 and NALM-6 leukaemia cells and WM-115 melanoma cells. Cytotoxic effectiveness of one of these complexes against melanoma WM-115 cells was two times higher than that of cisplatin. The protonation constant log K=9.63 of ligand b corresponding to the phenol 2-hydroxy group has been determined in 10% (v/v) DMSO/water solution (25°C). The coordination modes (formation of two monomeric species: NiL and NiL(2)) in the complexes with Ni(II) are discussed for b on the basis of the potentiometric and UV/Vis data.

Coordinative interaction of microcrystalline chitosan with oxovanadium (IV) ions in aqueous solution.

BackgroundChitosan, a non-toxic, biodegradable and biocompatible polysaccharide has attained great interest in pharmaceutical applications, as versatile drug delivery agent. Chitosan has been already shown to serve as vehicle for sustained drug release by chitosan-vanadium(IV) complex from a chitosan gel matrix. Therefore, chitosan gel proved to retain vanadium and preserve its insulin-mimetic efficacy. Nevertheless, there is a lack of reports concerning complexing equilibria in aqueous solution, in particular when using the more advantageous microcrystalline form of chitosan (MCCh). Microcrystalline chitosan shows a number of valuable features as compared with unmodified chitosan.ResultsExperimental studies on complexing interaction between a special form of biomaterial - microcrystalline chitosan as ligand, L = MCCh, of two exemplary degrees of deacetylation DD (lower 79.8%; higher 97.7%) with M = oxovanadium (IV) ions have been carried out potentiometrically at four ligand-to-metal concentration ratios (2:1, 5:1, 8:1, 10:1). Among the five hydrolysis equilibria of VO2+ reported up to now in the literature, under the conditions of the present work i.e. aqueous solutions of ionic strength I = 0.1 (KNO3) and temperature 25.0 ± 0.1°C, the predominating one was (VO)2(OH)22+ formation: log β20-2 = -7.01(2). Analysis of potentiometric results permitted to note that degree of deacetylation does not essentially influence the coordination mode of the complexes formed. In the case of both the two DD values, as well as for all the ligand-to-metal ratios, formation of hydroxyl deprotonated MLH-1 and ML2H-2 moieties has been confirmed potentiometrically (log β11-1 = -0.68(2) for DD = 79.8% and -0.68(2) for DD = 97.7%, log β12-2 = -7.64(6) for DD = 79.8% and -5.38(7) for DD = 97.7%).ConclusionMicrocrystalline chitosan coordinates the vanadyl ions by the hydroxyl groups. Interaction of MCCh with VO2+ ions in aqueous solution occurs within pH 5-7. Amounts of alkali excessive towards -NH2 are needed to deprotonate the OH groups. Deprotonation occurring at the chitosan hydroxyl groups permits a “pendant” or “bridge” model of coordination with VO(IV). Lack of complexation via deprotonation of amine groups, typical for simple cations and the molybdenum anion, has been indicated also by FTIR spectroscopy and EPR.

Studies on the cobalt(II)-dipeptide-imidazole system; a new dioxygen carrier

Abstract A series of new mixed cobalt(II) complexes with dipeptide and imidazole, which are dioxygen carriers, was synthesized. The oxygen-free, high-spin octah

Detection of Nitrate(NO-2) Ions Produced in Disproportionation of Nitrogen(II) Oxide in Aqueous Solution

Detection of Nitrate(NO-2) Ions Produced in Disproportionation of Nitrogen(II) Oxide in Aqueous Solution The nitrate ions (NO-2), products of disproportionation of NO in aqueous solution, were detected by an Orion Nitrite Electrode 97-46. Calibrations by means of standard NaNO2 solutions within the range 0.001÷100 ppm indicated linear dependence of EMF on ppm within 1÷100 ppm. Measurements justified the usefulness of this detection method of NO in solutions of OH- concentration lower than 10-2 mol dm-3 since at higher concentrations the EMF values exceeded the measurement range of the electrode. Occurrence of nitrate ions produced in the disproportionation reaction was additionally confirmed in dependence of OH- concentration by near UV and fluorescence spectra. The calibrated ion-selective nitrate electrode has also been shown, on the basis of Co(II)-dipeptide-OH- systems, as a useful tool in studying reversible NO uptake by Co(II) chelates in aqueous solution. Such a reaction may be regarded as simulating the harmful binding of NO by hemoglobin, where it substitutes the isoelectronic dioxygen. Detekcja Jonów Azotanowych (NO-2) Powstających W Reakcji Dysproporcjonowania Tlenku Azotu(II) W Roztworze Wodnym Jony azotanowe (NO-2), produkty dysproporcjonowania NO w roztworze wodnym, oznaczano za pomocą jonoselektywnej elektrody Orion Nitride Electrode 97-46. Kalibracje za pomocą standardowych roztworów NaNO2 w zakresie 0.001÷100 ppm wskazywały liniową zależność SEM od ppm w zakresie 1÷100 ppm. Pomiary uzasadniły użyteczność tej metody wykrywania NO w roztworach o stężeniu OH- mniejszym niż 10-2 mol dm-3, ponieważ przy większych stężeniach wartości SEM przekraczały zakres pomiarowy elektrody. Występowanie jonów azotanowych tworzonych w reakcji dysproporcjonowania było dodatkowo potwierdzane, w zależności od stężenia OH-, za pomocą widm w bliskim UV i widm fluorescencyjnych. Wykazano także, na przykładzie układów Co(II)-dipeptyd-OH-, że kalibrowana jonoselektywna elektroda na jony azotanowe (NO-2) może być użytecznym narzędziem w badaniu odwracalnego wiązania NO przez chelaty Co(II) w roztworze wodnym, reakcji symulującej szkodliwe działanie tlenku azotu(II) na hemoglobinę.

The distinctive properties of dioxygen complexes formed in the cobalt(II)-asparagine-OH− systems (in relation to other amino acids and mixed complexes with N-base)

Abstract Dioxygen complexes forming in the Cobalt(II)-asparagine-OH− system in aqueous solution have been investigated by potentiometric, volumeric and spectroscopic methods. In contrast to the corresponding complexes with other bidentate amino acids the asparagine ligand acts at high pH (> 13) as a tridentate ligand, the stability of the oxygen adduct being evidently enhanced thereby. This result has been interpreted as coordination of the side chain amide group deprotonated in presence of the metal, followed by structurally stimulated formation of a monobridged dimer. Additionally it has been proved that in weakly basic solutions the cobalt(II)-α-amino acid active complexes, able to bind dioxygen, are generally of ML3 type (not ML2 as it was assumed up to now).

Complexes in aqueous cobalt(II)–2-picolinehydroxamic acid system: Formation equilibria, DNA-binding ability, antimicrobial and cytotoxic properties

The coordination properties of 2-picolinehydroxamic acid towards cobalt(II) in aqueous solution were determined by a pH-metric method and confirmed by spectroscopic (UV-Vis and ESI-MS) studies. The results show the formation of mononuclear complexes, as well as of metallacrowns (MC). All methods indicate a high tendency of 2-picolinehydroxamic acid to form cobalt(II) metallacrown 12-MC-4. ESI-MS additionally confirms 15-MC-5 and 18-MC-6, stabilized by a sodium ion and methanol. The complexes observed in the speciation model at a pH about 7.2 were studied for their DNA-binding ability. The decrease of absorbance in the range of ca 310-400 nm indicates effective binding to calf thymus DNA by 2-picolinehydroxamic acid complexes, via intercalative mode. The antimicrobial properties of 2-picolinehydroxamic acid, cobalt(II) ions and of the complexes formed in the Co(II) - ligand system were determined against Gram-positive bacteria (Enterococcus faecalis, Enterococcus faecium, Staphylococcus aureus, Bacillus subtilis), Gram-negative bacteria (Pseudomonas aeruginosa, Escherichia coli, Helicobacter pylori) and fungal strains (Candida, Aspergillus niger). The results indicate that the complexes demonstrate greater antibacterial and antifungal activity for most strains than the ligand. Both the complexes and the ligand induce a slight decrease in the metabolic activity of cells, while the complexes do not damage the cell nuclei. The 2-picolinehydroxamic acid complexes activate the human monocytic cells, suggesting they have immunomodulating properties, which are particularly important in combating infections caused by strains resistant to other drugs.