Synthesis and Structure of Novel Copper(II) Complexes with N,O- or N,N-Donors as Radical Scavengers and a Functional Model of the Active Sites in Metalloenzymes.

To evaluate the antioxidant activity of potential synthetic enzyme mimetics, we prepared new five copper(II) complexes via a self-assembly method and named them [Cu(2-(HOCH2)py)3](ClO4)2 (1), [Cu(2-(HOCH2)py)2(H2O)2]SiF6 (2), [Cu2(2-(HOCH2CH2)py)2(2-(OCH2CH2)py)2](ClO4)2 (3), [Cu(pyBIm)3](BF4)2·1.5H2O (4) and [Cu(py2C(OH)2)2](ClO4)2 (5). The synthetic protocol involved N,O- or N,N-donors: 2-(hydroxymethyl)pyridine (2-(HOCH2)py), 2-(hydroxyethyl)pyridine (2-(HOCH2CH2)py), 2-(2-pyridyl)benzimidazole (pyBIm), di(2-pyridyl)ketone (py2CO). The obtained Cu(II) complexes were fully characterised by elemental analysis, FTIR, EPR, UV-Vis, single-crystal X-ray diffraction and Hirshfeld surface analysis. Crystallographic and spectroscopic analyses confirmed chromophores of both monomeric ({CuN3O3} (1), {CuN2O4} (2), {CuN6} (4), {CuN4O2} (5)) and dimeric complex ({CuN2O3} (3)). Most of the obtained species possessed a distorted octahedral environment, except dimer 3, which consisted of two copper centres with square pyramidal geometries. The water-soluble compounds (1, 3 and 5) were selected for biological testing. The results of the study revealed that complex 1 in solutions displayed better radical scavenging activity than complexes 3, 5 and free ligands. Therefore, complex 1 has been selected for further studies to test its activity as an enzyme mimetic. The chosen compound was tested on the erythrocyte lysate of two groups of patients after undergoing chemotherapy and chemoradiotherapy. The effect of the tested compound (1) on enzyme activity levels (TAS, SOD and CAT) suggests that the selected complex can be treated as a functional mimetic of the enzymes.

Structural Insights into New Bi(III) Coordination Polymers with Pyridine-2,3-Dicarboxylic Acid: Photoluminescence Properties and Anti-Helicobacter pylori Activity.

Two novel coordination polymers, [Bi2(2,3pydc)2(2,3pydcH)2(H2O)]n (1) and {(Et3NH)2[Bi(2,3pydc)(2,3pydcH)Cl2]}n (2) were prepared using as a prolinker pyridine-2,3-dicarboxylic acid (2,3pydcH2). The obtained complexes were fully characterized by elemental analysis, TG/DTG, FT-IR, solid-state photoluminescence, DFT calculations and single-crystal X-ray diffraction. The obtained complexes crystallized in the triclinic P-1 space group (1) and comprise dimeric units with two crystallographically different Bi(III) centers (polyhedra: distorted pentagonal bipyramid and bicapped trigonal prism) and monoclinic P21/c space group (2) with a distorted monocapped pentagonal bipyramid of Bi(III) center. The various coordination modes of bridging carboxylate ligands are responsible for the formation of 1D chains with 4,5C10 (1) and 2C1 (2) topology. The photoluminescence quantum yield for polymer 2 is 8.36%, which makes it a good candidate for more specific studies towards Bi-based fluorescent materials. Moreover, it was detected that polymer 1 is more than twice as active against H. pylori as polymer 2. It can be concluded that there is an existing relationship between the structure and the antibacterial activity because the presence of chloride and triethylammonium ions in the structure of complex 2 reduces the antibacterial activity.

Ruthenium(II) and Iridium(III) Complexes as Tested Materials for New Anticancer Agents.

The oncological use of cisplatin is hindered by its severe side effects and a very important resistance problem. To overcome these problems, scientists have attempted to design new generation transition-metal anticancer complexes. In this study, we present new complexes, ruthenium(II) [(η6-p-cymene)RuCl(py2CO)]PF6 (1), iridium(III) [(η5-Cp)IrCl(py2CO)]PF6 (2), and NH4[IrCl4(py2CO)]·H2O (3), based on di-2-pyridylketone (py2CO). The prepared complexes were characterized by FTIR, 1H, 13C, 15N NMR, UV-Vis, PL and elemental analysis techniques. The single-crystal X-ray structure analysis and comparative data revealed pseudo-octahedral half-sandwich 1 and 2 complexes and octahedral tetrachloroiridate(III) 3 with a rare chelating κ2N,O coordination mode of py2CO. The compounds were tested in vitro against three cancer cell lines-colorectal adenoma (LoVo), myelomonocytic leukaemia (MV-4-11), breast adenocarcinoma (MCF-7), and normal fibroblasts (BALB/3T3). The most promising results were obtained for iridium(III) complex 3 against MV-4-11 (IC50 = 35.8 ± 13.9 µg/mL) without a toxic effect against normal BALB/3T3, which pointed towards its selectivity as a potential anticancer agent. Extensive research into their mode of binding with DNA confirmed for 1 and 2 complexes non-classical binding modes, while the 3D circular dichroism (CD) experiment (ΔTm) suggested that 3 induced the probable formation of covalent bonds with DNA. In addition, the obtained iridium complexes induce ROS, which, in synergy with hydrolysis promoting DNA bonding, may lead to cancer cell death.

Synthesis, Structural Characterization and Antimicrobial Evaluation of Ruthenium Complexes with Heteroaromatic Carboxylic Acids.

The antibacterial and antibiofilm activities of two new ruthenium complexes against E. coli, S. aureus, P. aeruginosa PAO1 (laboratory strain) and P. aeruginosa LES B58 (clinical strain) were evaluated. Complexes, mer-[RuIII (2-bimc)3 ] ⋅ H2 O (1) and cis-[RuIV Cl2 (2,3-pydcH)2 ] ⋅ 4H2 O (2), were obtained using aromatic carboxylic acid ligands, namely, 1H-benzimidazole-2-carboxylic acid (2-bimcH) and pyridine-2,3-dicarboxylic acid (2,3-pydcH2 ). Compounds were physicochemically characterized using X-ray diffraction, Hirshfeld surface analysis, IR and UV/VIS spectroscopies, as well as magnetic and electrochemical measurements. Structural characterization revealed that Ru(III) and Ru(IV) ions in the complexes adopt a distorted octahedral geometry. The intermolecular classical and weak hydrogen bonds, and π⋅⋅⋅π contacts significantly contribute to structure stabilization, leading to the formation of a supramolecular assembly. Biological studies have shown that the Ru complexes inhibit the growth of bacteria and biofilm formation by the tested strains and the complexes seem to be a potential as antimicrobial agents.

Similarities and differences in d6 low-spin ruthenium, rhodium and iridium half-sandwich complexes: synthesis, structure, cytotoxicity and interaction with biological targets.

In this paper, we discussed the similarities and differences in d6 low-spin half-sandwich ruthenium, rhodium and iridium complexes containing 2,2'-biimidazole (H2biim). Three new complexes, {[RuCl(H2biim)(η6-p-cymene)]PF6}2·H2O (1), [(η5-Cp)RhCl(H2biim)]PF6 (2), and [(η5-Cp)IrCl(H2biim)]PF6 (3), were fully characterized by CHN, X-ray diffraction analysis, UV-Vis, FTIR, and 1H, 13C and 15N NMR spectroscopies. The complexes exhibit a typical pseudooctahedral piano-stool geometry, in which the aromatic arene ring (p-cymene or Cp) forms the seat, while the bidentate 2,2'-biimidazole and chloride ion form the three legs of the piano stool. Moreover, the cytotoxic activities of the compounds were examined in the LoVo, HL-60, MV-4-11, MCF-7 human cancer cell lines and BALB/3T3 normal mouse fibroblasts. Notably, the investigated complexes showed no cytotoxic effects towards the normal BALB/3T3 cell line compared to cisplatin, which has an IC50 value of 2.20 µg. Importantly, 1 displayed the highest activity against HL-60 (IC50 4.35 µg). To predict a binding mode, we explored the potential interactions of the metal complexes with CT-DNA and protein using UV absorption and circular dichroism. The obtained data suggest that the complexes could interact with CT-DNA via an outside binding mode. Moreover, binding of the complexes with the GSH via UV-Vis and ESI mass spectra was determined. Comparative studies have shown that the rhodium complex (2) is the most GSH reactive, which is probably responsible for its deactivation towards LoVo and MCF-7 tumour cells. The influence of the metal ion on the biological activity of isostructural Rh(III) and Ir(III) complexes was an important goal of the presented investigation.

Recent Research Trends on Bismuth Compounds in Cancer Chemoand Radiotherapy.

BACKGROUND: Application of coordination chemistry in nanotechnology is a rapidly developing research field in medicine. Bismuth complexes have been widely used in biomedicine with satisfactory therapeutic effects, mostly in Helicobacter pylori eradication, but also as potential antimicrobial and anti-leishmanial agents. Additionally, in recent years, application of bismuth-based compounds as potent anticancer drugs has been studied extensively. METHODS: Search for data connected with recent trends on bismuth compounds in cancer chemo- and radiotherapy was carried out using web-based literature searching tools such as ScienceDirect, Springer, Royal Society of Chemistry, American Chemical Society and Wiley. Pertinent literature is covered up to 2016. RESULTS: In this review, based on 213 papers, we highlighted a number of current problems connected with: (i) characterization of bismuth complexes with selected thiosemicarbazone, hydrazone, and dithiocarbamate classes of ligands as potential chemotherapeutics. Literature results derived from 50 papers show that almost all bismuth compounds inhibit growth and proliferation of breast, colon, ovarian, lung, and other tumours; (ii) pioneering research on application of bismuth-based nanoparticles and nanodots for radiosensitization. Results show great promise for improvement in therapeutic efficacy of ionizing radiation in advanced radiotherapy (described in 36 papers); and (iii) research challenges in using bismuth radionuclides in targeted radioimmunotherapy, connected with choice of adequate radionuclide, targeting vector, proper bifunctional ligand and problems with 213Bi recoil daughters toxicity (derived from 92 papers). CONCLUSION: This review presents recent research trends on bismuth compounds in cancer chemo- and radiotherapy, suggesting directions for future research.

Synthesis and physicochemical characterization of two lead(II) complexes with O-, N-donor ligands. Lone pair functionality and crystal structure.

A dinuclear [Pb2(4-CHO-5-MeIm)6(NO3)2](NO3)2 (1) and a polynuclear [Pb(2-pzc)2(H2O)]n (2) complexes (where 5(4)-carbaldehyde-4(5)-methylimidazole (5(4)-CHO-4(5)-MeIm) and pyrazine-2-carboxylic acid (2-pzcH)) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray crystallography. Structural determination for complex 1 reveals a cationic species [Pb(4-CHO-5-MeIm)3]2+ connected through bridging nitrate(V) ions. There are also an uncoordinated nitrate ions as counterions. Complex 2 is a three-dimensional architecture consisting of Pb6O12 building units. The pyrazine-2-carboxylato ligand behaves as a chelating agent and a bi-connective bridge. The coordination polyhedra around lead(II) ion could be described as a distorted docecahedron (1) or monocapped trigonal prism (2). The luminescent properties of 1 and 2 investigated in the solid state at room temperature indicate structure-dependent photoluminescent properties. The DFT calculations and the X-ray structural data point on rather hemidirected type of coordination around Pb(II) ions of 1 and 2.

Eight- and six-coordinated Mn(II) complexes of heteroaromatic alcohol and aldehyde: crystal structure, spectral, magnetic, thermal and antibacterial activity studies.

Crystal, molecular and electronic structure of new manganese(II) compounds: [Mn(2-CH2OHpy)2(NO3)2] (1), [Mn(4-CHO-5-MeIm)2(NO3)2] (2) and [Mn(4-CHO-5-MeIm)2Cl2] (3), where 2-hydroxymethylpyridine (2-CH2OHpy) and 5(4)-carbaldehyde-4(5)-methylimidazole (5(4)-CHO-4(5)-MeIm), have been characterised using X-ray, spectroscopic, magnetic and TG/DTG data. In compounds 1 and 2, the Mn(II) ion is eight-coordinated forming distorted pseudo-dodecahedron, that is rather unusual for the manganese(II) complexes, whereas in 3 the Mn(II) ion environment is a distorted octahedron. The high coordination number (CN=8) of 1 and 2 results from bidentate character of the nitrate ligands. The X-band EPR spectra of compounds 2 and 3 exhibit fine structure signals resulting from zero-field splitting (ZFS) of the spin states for high spin d(5) Mn(II), whereas for 1 the broad isotropic signals were observed. The estimation of ZFS for individual Mn(II) ions was carried out for all compounds using DFT calculations. The free ligands and their manganese(II) complexes have been tested in vitro against gram-positive and gram-negative bacteria in order to assess their antimicrobial properties.

A novel single-site manganese(II) complex of a pyridine derivative as a catalase mimetic for disproportionation of H2O2 in water.

A novel single site Mn(II) complex was successfully synthesized and tested in the aqueous disproportionation of hydrogen peroxide. The complex was found to be stable (HR-XAS) and exhibits catalase-like activity in neutral pH. Theoretical calculations suggested a reaction mechanism involving two complexes, changes in metal oxidation state and proton shuttling.

Ruthenium complexes in different oxidation states: synthesis, crystal structure, spectra and redox properties.

The reactions of a mother solution of RuCl(3) with benzimidazole derivatives 2-(2'-pyridyl)benzimidazole (2,2'-PyBIm, L(1)) and 2-hydroxymethylbenzimidazole (2-CH(2)OHBIm, L(2)) yielded three novel ruthenium complexes: (H(2)L(1))(2)[Ru(III)Cl(4)(CH(3)CN)(2)](2)[Ru(IV)Cl(4)(CH(3)CN)(2)]·2Cl·6H(2)O (1), mer-[Ru(III)Cl(3)L(1)(CH(3)CN)]·L(1)·3H(2)O (2), and (HL(2))(4)[Ru(IV)Cl(6)]·2Cl·4H(2)O (3). The isolated compounds were characterised by elemental analyses, UV-Vis and IR spectroscopy, and magnetic measurements. The nature of the ligands bound to the metal ions of these compounds and the experimental conditions significantly influenced the ruthenium complexes in different oxidation states. The N,N-donor ligand bound to the metal centre is a recognised stabiliser of the +III state of ruthenium, whereas the lack of ligand coordination promotes the formation of a mixed (Ru(III)/Ru(IV)) complex. In the case of complex 3, the absence of a N,O-donor ligand in the coordinate sphere facilitates the formation of the compound in a higher oxidation state. X-ray single crystal analyses revealed an octahedral geometry in each of the complexes. The crystal structure of ruthenium complexes is formed by a network of intermolecular classical and unconventional (C-H···π) hydrogen bonds. The most interesting feature of the supramolecular architecture of complexes is the existence of a very rare Cl(-)···π interaction and π···π stacking, which also contribute to structural stabilisation. Ruthenium compounds 2 and 3 behave as paramagnets with an octahedral geometry, corresponding to the presence of one or two unpaired electrons, respectively. The cyclic voltammetric data of complex 2 show three one-electron redox processes. The first redox couple is reversible, whereas the two other couples have a quasi-reversible nature. In the case of complex 3, two redox couples are reversible and the electrode processes are connected with exchange of one electron.

Assembling novel Cd(II) complexes with multidentate nitrogen donor ligands obtained in situ from the system: zerovalent copper, cadmium oxide, 1-hydroxymethyl-3,5-dimethylpyrazole and ammonium thiocyanate.

A novel 3D coordination polymer [Cd2(L(1))(2)(SCN)(4)(MeOH)(2)](n) (1) and monomeric [Cd(NCS)(2)L(2)] (2) (L(1) = urotropine, L(2) = tris(1-(3,5-dimethylpyrazolylmethyl))amine) have been prepared in a one-pot synthesis using 1-hydroxymethyl-3,5-dimethylpyrazole as the starting ligand. The most prominent feature is the formation in situ of the organic compounds: urotropine and scorpionate-tripodal ligands.

[Dietary habits and nutritional status of secondary school pupils]. / Zwyczaje zywieniowe i stan odzywienia mlodziezy w wieku 13-15 lat Gimnazjum w Niepolomicach.

Proper nutrition is one of the main factors which influence peoples harmonious development. Teenagers media promote the patterns of physical appearance and behaviour that can cause and strengthen inadequate nourishment habits. People having problems with self-esteem may develop dangerous dysfunctions like anorexia or bulimia. The aim of this work was checking the number and quality of meals eaten by 13-15 year old student of secondary school in Niepolomice. A research has been carried out among two hundred students (111 girls and 89 boys) The way of nutrition on the basis of the questionnaire by Starzynska and the frequency of incorrect nutritional behaviors on the basis of Eating Attitudes Test-26 (EAT26) were estimated. It was revealed too small consumption of dairy products, whole meal bread, and pulse crops. Such diet lowers nutritive and mineral components in organism. It may effect further health condition of grown people. Girls are more liable to suffer from the negative influence of media because it is a lot more difficult for them to accept their figure. Also disturbed eating attitudes and behaviour are observed particularly among girls in adolescence period.