Chiral Sulfoximine Mediated Cobalt-Catalyzed Atropselective C-H Annulation of Ynamides.

An achiral Cp*Co(III)-catalyzed enantioselective C-H activation/annulation of chiral sulfoximine-enabled thioamides with ynamides is presented herein. This method successfully synthesizes axially chiral five-membered 2-amidoindenones with good enantiocontrol. Interestingly, the annulation with chiral oxazolidone-containing ynamides could provide a separable mixture of diastereomers (up to ~10:1 dr). Moreover, enantiopure sulfoximines could be recovered with ~99% purity, making this method practical. DFT studies show valuable insight into the mechanism and origin of asymmetric induction.

Anticancer, antimicrobial and photocatalytic activities of a new pyrazole containing thiosemicarbazone ligand and its Co(III) and Ni(II) complexes: Synthesis, spectroscopic characterization and X-ray crystallography.

A new pyrazole based thiosemicarbazone ligand, 5-methyl-3-formylpyrazole-N(4)-isopropylthiosemicarbazone, (HMPzNHPri) (compound I), and its cobalt(III) and nickel(II) complexes, [Co(MPzNHPri)2]Cl (compound II) and [Ni(HMPzNHPri)2]Br2 (compound III), respectively, have been synthesized and characterized through various physico-chemical and spectroscopic studies. Both the reported Co(III) and Ni(II) complexes are cationic in nature and behave as 1:1 and 1:2 electrolytes in MeOH, respectively. Electronic spectral features of the complexes have classified them as distorted octahedral ones. IR spectral data (4000-450 cm-1) have suggested a monoprotic tridentate (NNS) function of compound I coordinating to the Co(III) ion via the pyrazolyl (tertiary) ring nitrogen, azomethine nitrogen and thiolato sulphur atom; while for compound III, compound I has been found to act as neutral NNS tridentate one, coordinating to Ni(II) via the pyrazolyl iminic nitrogen, azomethine nitrogen and thioketo sulphur. Structural features of all the compounds are confirmed by the single crystal X-ray data. All the compounds reported here have been found to exhibit significant photocatalytic activity towards degradation of Methylene Blue (MB) under UV radiation. Anticancer activity of all the three compounds against cancer cell lines (HeLa and A549) and a normal cell line (HEK293) have been investigated. Compound II has been found to be more efficient against the human cervical cancer cell (HeLa) and the lung cancer cell (A549) than compounds I and III. The ligand and both the complexes display potential activities against both gram-positive (Bacillus subtilis MTCC 7193) and gram-negative bacteria (E. coli MTCC 1610).

Engineering the Co(II)/Co(III) Redox Cycle and Coδ+ Species Shuttle for Nitrate-to-Ammonia Conversion.

Electroreduction of waste nitrate to valuable ammonia offers a green solution for environmental restoration and energy storage. However, the electrochemical self-reconstruction of catalysts remains a huge challenge in terms of maintaining their stability, achieving the desired active sites, and managing metal leaching. Herein, we present an electrical pulse-driven Co surface reconstruction-coupled Coδ+ shuttle strategy for the precise in situ regulation of the Co(II)/Co(III) redox cycle on the Co-based working electrode and guiding the dissolution and redeposition of Co-based particles on the counter electrode. As result, the ammonia synthesis performance and stability are significantly promoted while cathodic hydrogen evolution and anodic ammonia oxidation in a membrane-free configuration are effectively blocked. A high rate of ammonia production of 1.4 ± 0.03 mmol cm-2 h-1 is achieved at -0.8 V in a pulsed system, and the corresponding nitrate-to-ammonia Faraday efficiency is 91.7 ± 1.0%. This work holds promise for the regulation of catalyst reactivity and selectivity by engineering in situ controllable structural and chemical transformations.

Simultaneous spectrophotometric determination of Co (II) and Co (III) in acidic medium with partial least squares regression and artificial neural networks.

This study aims at the application of two chemometric techniques to visible spectra of acetic acid solutions of Co (II) and Co (III) for simultaneous determination thereof. Spectral data of 145 samples in the range of 400-700 nm were used to build the models. Partial least squares regression models were developed for which latent variables were determined using internal cross-validation with a leave-one-out strategy and 3 and 2 latent variables were selected for Co(II) and Co(III) based on root mean square error of cross-validation. For these models, root mean square errors of prediction were 1.16 and 0.536 mM and coefficients of determination were 0.975 and 0.892 for Co (II) and Co (III). As an alternate method, artificial neural networks consisting of three layers, with 10 neurons in hidden layer, were trained to model spectra and concentrations of cobalt species. Levenberg-Marquardt algorithm with feed-forward back-propagation learning resulted root mean square errors of prediction of 0.316 and 0.346 mM for Co (II) and Co (III) respectively and coefficients of determination were 0.996 and 0.988.

Monoethanolamine enhanced iohexol degradation in the Co(II)/sulfite system: Nonnegligible role of complexation in accelerating cobalt redox cycling.

Generation of sulfate radicals (SO4•-) from sulfite activation has emerged as a promising method for abatement of organic pollutants in the water and wastewater treatment. Co(II) has garnered attention due to its high catalytic activity in the sulfite activation, which is compromised by the slow Co(II)/Co(III) redox cycling. Regarding the regulation of Co(II) electronic structure via the complexation effect, monoethanolamine (MEA), a common chelator, is introduced into the Co(II)/sulfite system. MEA addition results in a significant improvement in iohexol abatement efficiency, increasing from 40% to 92%. The superior iohexol abatement relies on the involvement of SO4•-, hydroxyl radicals (HO•) and Co(IV). Hydrogen radical (•H) is unexpectedly detected, acting as a strong reducing agent, contributing to the reduction of Co(III). This enhancement of sulfite activation by MEA is due to the formation of the Co(II)-MEA complex, in which the complexation ratio of Co(II) and MEA is critical. Electrochemical characterization and theoretical calculations demonstrate that the complexation can facilitate the Co(II)/Co(III) redox cycling with the concomitant enhancement of sulfite activation. This work provides a new insight into the Co(II)/sulfite system in the presence of organic ligands.

Ru(II) Oxygen Sensors for Co(III) Complexes and Amphotericin B Antifungal Activity Detection by Phosphorescence Optical Respirometry.

The measurement of oxygen consumption is an important element in the understanding of an organism's metabolic state. Oxygen is also a phosphorescence quencher, which allows the evaluation of phosphorescence emitted by oxygen sensors. Two Ru(II)-based oxygen-sensitive sensors were used to study the effect of chemical compounds [(1) = [CoCl2(dap)2]Cl, and (2) = [CoCl2(en)2]Cl (AmB = amphotericin B) against reference and clinical strains of Candida albicans. The tris-[(4,7-diphenyl-1,10-phenanthroline)ruthenium(II)] chloride ([Ru(DPP)3]Cl2) (Box) adsorbed onto the DavisilTM silica gel was embedded in the silicone rubber Lactite NuvaSil® 5091 and the coating on the bottom of 96-well plates. The water-soluble oxygen sensor (BsOx = tris-[(4,7-diphenyl-1,10-phenanthrolinedisulphonic acid disodium)ruthenium(II)] chloride 'x' hydrate = {Ru[DPP(SO3Na)2]3}Cl2 = water molecules were omitted in the BsOx formula) was synthesized and characterized by RP-UHPLC, LCMS, MALDI, elemental analysis, ATR, UV-Vis, 1H NMR, and TG/IR techniques. The microbiological studies were performed in the environment of RPMI broth and blood serum. Both Ru(II)-based sensors turned out to be useful in the study of the activity of Co(III) complexes and the commercial antifungal drug amphotericin B. In addition, a new activity of the oxygen sensor, the soluble Ru(II) complex BsOx, was demonstrated, which is a mixture with amphotericin B that caused a significant increase in its antifungal activity. Thus, it is also possible to demonstrate the synergistic effect of compounds active against the microorganisms under study.

Molecular Recognition of Imidazole-Based Drug Molecules by Cobalt(III)- and Zinc(II)-Coproporphyrins in Aqueous Media.

The methods of 1H NMR, spectrophotometric titration, mass spectrometry and elemental analysis are applied to determine the selective binding ability of Co(III)- and Zn(II)-coproporphyrins I towards a series of imidazole-based drug molecules with a wide spectrum of pharmacological activity (metronidazole, histamine, histidine, tinidazole, mercazolil, and pilocarpine) in phosphate buffer (pH 7.4) simulating the blood plasma environment. It is shown that in aqueous buffer media, Co(III)-coproporphyrin I, unlike Zn(II)-coproporphyrin I, binds two imidazole derivatives, and the stability of mono-axial Co-coproporphyrin imidazole complexes is two to three orders of magnitude higher than that of similar complexes of Zn-coproporphyrin I. The studied porphyrinates are found to have the highest binding ability to histamine and histidine due to the formation of two additional hydrogen bonds between the carboxyl groups of the porphyrinate side chains and the binding sites of the ligands in the case of histidine and a hydrogen bond between the amino group of the ligand and the carbonyl oxygen atom of the carboxyl group of the porphyrinate in the case of histamine. The structures of the resulting complexes are optimized by DFT quantum chemical calculations. The results of these studies may be of use in the design of biosensors, including those for the detection, control and verification of various veterinary drug residues in human food samples.

Coupling the effect of Co and Mo on peroxymonosulfate activation for the removal of organic pollutants.

Although heterogeneous cobalt-based catalysts have been widely studied and used in SO4•- based advanced oxidation processes, the efficiencies were still not high enough due to the limiting step of Co(III)/Co(II) cycle in the system. In this study, a bimetallic oxide composed of Co and Mo was designed and used for enhancing the performance of peroxymonosulfate activation on organic pollutants removal. The CoMoO4 nanorods exhibited superior catalytic activity for methylene blue (MB) degradation than Co3O4, MoO3, and their mechanical mixture, which was attributed to the synergetic effect between Co and Mo. CoMoO4 nanorods were able to efficiently degrade MB under a wide pH range of 3-11 and could maintain high efficiency in 5 cycles with less leakage of metal ions. Moreover, CoMoO4 nanorods displayed broad spectrum applicability to the different water matrix and a variety of pollutants such as phenol and Congo red. The Co(II) was proved to be the main active site of the catalyst, while Mo played an important role in promoting the Co(III)/Co(II) cycle. Surface free radicals are the main active species in the degradation process. This work provides new insights into the design of cobalt-based bimetallic catalyst and the improvement on PMS activation.

Embedding Co in perovskite MoO3 for superior catalytic oxidation of refractory organic pollutants with peroxymonosulfate.

A cobalt (Co)-doped perovskite molybdenum trioxide (α-MoO3) catalyst (Co-MO) was synthesized by a facile pyrolysis strategy and used for degrading various organic contaminants via peroxymonosulfate (PMS) activation. The doped Co was inserted in the inter space between the octahedron [MoO6], facilitating the growth of the α-MoO3 crystal on the [010] direction. This unique structure accelerated the activation of PMS as the Co-MO could function as a carrier for electron transfer to facilitate the Co(II)/Co(III) cycle in the Co-MO/PMS system. As a result, the Co-MO/PMS system showed noticeable activity for removing 100% bisphenol A (BPA) under a broad conditions within 30 min. The radical quenching test and electron paramagnetic resonance analysis revealed that singlet oxygen (1O2) was the main active species for BPA degradation in the Co-MO/PMS system, while free radicals, such as O2•-, SO4•- and •OH, were also produced as the intermediate species. Furthermore, the carrier mechanism may enable the Co-MO/PMS system maintain relatively high performance during repeat use, and also excellent adaptability was revealed by the well function in various water matrices and high activity in degrading various refractory organic pollutants. Our findings pave a useful avenue for the rational design of novel cobalt-doped catalysts with high catalytic performance toward wide environmental applications.

DNA interaction studies of a cobalt(III) complex containing ß-amino alcohol ligand by spectroscopic and molecular docking methods.

In the present research, the feasibility of a Cobalt(III) complex containing ß-amino alcohol ligands for affinity with the target calf thymus DNA is demonstrated. In the title complex, [Co(C11H15N2O2)2]Cl, the Co(III) atom is six-coordinated with four N atoms and two O atoms from (2-[(E)-({2-[(2-Hydroxyethyl) amino]ethyl}imino)methyl]phenol) ligand (L). To investigate the molecular interaction between the synthesized complex and DNA, some multi-spectroscopic approaches associated with molecular docking were employed in the physiological buffer (pH 7.4). The results indicated that the Co(III) complex proved to be a minor groove binder with a preference for the A-T region, which was substantiated by displacement studies with Hoechst33258 and Methylene blue (MB) as minor groove binder and intercalator. In addition, the results of the molecular docking study revealed that the Co(III) complex approached the gap between the DNA minor grooves near the spot where the Hoechst was. Furthermore, the results of the cytotoxicity and apoptosis tests for the MCF-7 cell line were also indicative of the positive effects of the complex on controlling the growth and viability of breast cancer.Communicated by Ramaswamy H. Sarma.

Experimental and theoretical studies of new Co(III) complexes of hydrazide derivatives proposed as multi-target inhibitors of SARS-CoV-2.

Cobalt(III) complexes with Schiff base ligands derived from hydrazone, (HL 1 = (E)-N'-(3,5-dichloro-2-hydroxybenzylidene)-4-hydroxybenzohydrazide, HL 2 = (E)-N'-(3,5-dichloro-2-hydroxybenzylidene)-4-hydroxybenzohydrazide (3,5-dibromo-2-hydroxybenzylidene), and HL 3 = (E)-4-hydroxy-N'-(2-hydroxy-3-ethoxybenzylidene)benzohydrazide), were synthesized and characterized by elemental analysis, Fourier transform infrared (FT-IR) spectroscopy, UV-Vis spectroscopy, and cyclic voltammetry. X-ray diffraction was used to determine the single crystal structure of the complex (1). Co(III) was formed in a distorted, very regular octahedral coordination in this complex; three pyridine moieties complete this geometry. Schiff base complexes' redox behaviors are represented by irreversible (1), quasi-reversible (2), and quasi-reversible (3) voltammograms. A density functional theory (DFT)/B3LYP method was used to optimize cobalt complexes with a base set of 6-311G. Furthermore, fragments occupying the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were investigated at the same theoretical level. Quantum theory of atoms in molecules (QTAIM) computations were also done to study the coordination bonds and non-covalent interactions in the investigated structures. Hirshfeld surface analysis was used to investigate the nature and types of intermolecular exchanges in the crystal structure of the complex (1). The capacity of cobalt complexes to bind to the major protease SARS-CoV-2 and the molecular targets of human angiotensin-converting enzyme-2 (ACE-2) was investigated using molecular docking. The molecular simulation methods used to assess the probable binding states of cobalt complexes revealed that all three complexes were stabilized in the active envelope of the enzyme by making distinct interactions with critical amino acid residues. Interestingly, compound (2) performed better with both molecular targets and the total energy of the system than the other complexes.

Electrically supported mediator Co(II)-activated peroxydisulfate synergistic process for organic contaminants elimination.

Among homogeneous catalysts, cobalt ions exhibit ultra-high persulfate activation performance. In this work, an electrically supported medium Co(II) activated peroxydisulfate synergistic process was established to eliminate organic contaminants in water. The synergistic catalytic effect was verified by comparing the oxidative degradation performance and reaction rate constant of different coupling systems. The decolorization ability of E-Co(II)-PDS on reactive black 5 (RB5) was explored, and the results showed that the removal rate of RB5 can reach 93.21% under the optimized conditions of current density of 5.71 mA/cm2, initial pH of 4, Co(II) concentration of 0.2 mM and PDS concentration of 5 mM. The effect of water matrix on the removal of RB5 was studied, and it was found that HCO3- and humic acid significantly inhibited the degradation of RB5, while Cl- and H2PO4- could effectively promote it at a certain concentration. Notably, the degradation of RB5 in E-Co(II)-PDS system achieved lower energy consumption, with an energy consumption per unit volume (EE/O) value of 0.4304 kWh·m-3. EPR test, quenching experiments and contribution rate analysis showed that the oxidation active species in E-Co(II)-PDS process were Co(III), sulfate radicals and hydroxyl radicals, and their oxidation contribution rates were 15.72%, 12.69% and 53.25%, respectively. Finally, the decomposition process of RB5 was proposed by the mass spectrometry results. The electric current promotes cobalt ion cycling and PDS activation through electron transfer, and induces Co(II) to promote the activation of PDS, which is the main mechanism of E-Co(II)-PDS system to achieve the robust degradation ability of RB5.

The First Dimeric Derivatives of the Glycopeptide Antibiotic Teicoplanin.

Various dimeric derivatives of the glycopeptide antibiotic teicoplanin were prepared with the aim of increasing the activity of the parent compound against glycopeptide-resistant bacteria, primarily vancomycin-resistant enterococci. Starting from teicoplanin, four covalent dimers were prepared in two orientations, using an α,ω-bis-isothiocyanate linker. Formation of a dimeric cobalt coordination complex of an N-terminal L-histidyl derivative of teicoplanin pseudoaglycone has been detected and its antibacterial activity evaluated. The Co(III)-induced dimerization of the histidyl derivative was demonstrated by DOSY experiments. Both the covalent and the complex dimeric derivatives showed high activity against VanA teicoplanin-resistant enterococci, but their activity against other tested bacterial strains did not exceed that of the monomeric compounds.

Antibacterial Activity of Co(III) Complexes with Diamine Chelate Ligands against a Broad Spectrum of Bacteria with a DNA Interaction Mechanism.

Cobalt coordination complexes are very attractive compounds for their therapeutic uses as antiviral, antibacterial, antifungal, antiparasitic, or antitumor agents. Two Co(III) complexes with diamine chelate ligands ([CoCl2(dap)2]Cl (1) and [CoCl2(en)2]Cl (2)) (where dap = 1,3-diaminopropane, en = ethylenediamine) were synthesized and characterized by elemental analysis, an ATR technique, and a scan method and sequentially tested against Gram-positive and Gram-negative bacteria. The minimum inhibitory concentration results revealed that anaerobic and microaerophilic bacteria were found to be the most sensitive; the serial passages assay presented insignificant increases in bacterial resistance to both compounds after 20 passages. The synergy assay showed a significant reduction in the MIC values of nalidixic acid when combined with Compounds (1) or (2). The assessment of cell damage by the complexes was performed using scanning electron microscopy, transmission electron microscopy, and confocal microscopy, which indicated cell membrane permeability, deformation, and altered cell morphology. DNA interaction studies of the Co(III) complexes with plasmid pBR322 using spectrophotometric titration methods revealed that the interaction between Complex (1) or (2) and DNA suggested an electrostatic and intercalative mode of binding, respectively. Furthermore, the DNA cleavage ability of compounds by agarose gel electrophoresis showed nuclease activity for both complexes. The results suggest that the effect of the tested compounds against bacteria can be complex.

Synergistic Effect of Co(III) and Co(II) in a 3D Structured Co3O4/Carbon Felt Electrode for Enhanced Electrochemical Nitrate Reduction Reaction.

As nitrate contamination causes serious environmental problems, it is necessary to develop stable and efficient electrocatalysts for efficient electrochemical nitrate reduction reaction (ENRR). Here, a nonprecious Co3O4/carbon felt (CF) electrode with a 3D structure was prepared by integrating electrodeposition with calcination methods. This 3D structured Co3O4/CF electrode exhibits a high-rate constant of 1.18 × 10-4 s-1 cm-2 for the ENRR, surpassing other Co3O4 electrodes in previous literature. Moreover, it also has an excellent stability with a decrease of 6.4% after 10 cycles. Density functional theory calculations, electron spin resonance analysis, and cyclic voltammetry were performed to study the mechanism of the ENRR on the Co3O4/CF electrode, proving that atomic H* (indirect pathway) plays a prominent role in NO3- reduction and clarifying the synergistic effect of Co(III) and Co(II) in the Co(II)-Co(III)-Co(II) redox cycle for the ENRR: Co(III) prefers the adsorption of NO3- and Co(II) favors the production of H*. Based on this synergy, a relatively large amounts of Co(II) on the surface of the Co3O4/CF electrode (1.3 Co(II)/Co(III) ratio) was maintained by controlling the temperature of calcination to 200 °C with a lower energy barrier of H* formation of 0.46 eV than other ratios, which is beneficial for forming H* and enhancing the performance of the ENRR. Thus, this study suggests that building 3D structure and optimizing Co(II)/Co(III) ratio are important for designing efficient Co3O4 electrocatalyst for ENRR.

Effect of the replacement of tripodal 4N donors by two 2N chelators on the redox and cytotoxic activity of maltolato and deferipronato containing Co(III) complexes.

Fourteen novel CoIII ternary complexes with the general formula [Co(4N)(2O)]X2 or [Co(2N)2(2O)]X2 where 4N = tris(2-aminoethyl)amine (tren) or tris(2-pyridylmethyl)amine (tpa); 2N = 1,10-phenantroline (phen), 2,2'-bipyridine (bipy), 1,2-diaminoethane (en) or 2-(aminomethyl)pyridine (ampy) and 2O = 1,2-dimethyl-3-hydroxy-4(1H)-pyridinone (dhpH), 3-hydroxy-2-methyl-4-pyrone (maltH) or 2-ethyl-3-hydroxy-4H-pyran-4-one (etmaltH) were synthesized, characterized and their redox features explored. Molecular structure of some selected [Co(2N)2(2O)](ClO4)2 (2N = phen, bipy, en; 2O = dhp, malt) or [Co(4N)(2O)](ClO4)2 (4N = tpa; 2O = etmalt) type complexes were assessed by X-ray diffraction and showed the expected octahedral geometry. Replacement of the 4N donor ligands by two 2N donor ligands resulted in the decrease of the cathodic peak potential of the complexes indicating easier reduction and allowing therefore the tailoring of the redox properties of the complexes. Screening of selected compounds against a human derived cancer cell line, HeLa, showed that, unlike the [Co(4N)(2O)]X2 derivatives, the complexes containing 2N = bipy or phen ligands have better anticancer activity than cisplatin or carboplatin.

Influence of Co(III) Polypyridyl Complexes on Luminescence Behavior, DNA Binding, Photocleavage, Antimicrobial Activity and Molecular Docking Studies.

A new ligand FIPB = 5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)furan-2-yl-2-boronic acid, having three cobalt(III) polypyridyl complexes [Co(phen)2(FIPB)]3+(1) {FIPB = 5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)furan-2-yl-2-boronic acid}, (phen = 1,10-Phenanthroline), [Co(bpy)2(FIPB)]3+(2) (bpy = 2,2'bipyridyl), [Co(dmb)2(FIPB)]3+(3) (dmb = 4, 4'-dimethyl 2, 2'-bipyridine) have been synthesized and characterized by elemental analysis, ES-MS,1H-NMR, 13C-NMR, UV-Vis and FTIR. Their DNA binding behavior has been explored by various spectroscopic titrations and viscosity measurements, which indicated that all the complexes bind to calf thymus DNA by means of intercalation with different binding strengths. The binding properties of these all three complexes towards calf-thymus DNA (CT-DNA) have been investigated by UV-visible, emission spectroscopy and viscosity measurements.The experimental results suggested that three Co(III) complexes can intercalate into DNA base pairs,but with different binding affinities. Photo induced DNA cleavage studies have been performed and results indicate that three complexes efficiently cleave the pBR322-DNA in different forms. The three synthesized compounds were tested for antimicrobial activity by using Staphylococcus aureus and Bacillus subtilis organisms, these results indicated that complex 1 was more activity compared to other two complexes against both tested microbial strains. The in vitro cytotoxicity of these complexes was evaluatedby MTT assay, and complex 1 shows higher cytotoxicity than complex 2 and 3 on HeLa cells.

Methyl transfer reactions catalyzed by cobalamin-dependent enzymes: Insight from molecular docking.

Methyl transfer reactions, mediated by methyltransferases (MeTrs), such as methionine synthase (MetH) or monomethylamine: CoM (MtmBC), constitute one of the most important classes of vitamin B12-dependent reactions. The challenge in exploring the catalytic function of MeTrs is related to their modular structure. From the crystallographic point of view, the structure of each subunit has been determined, but there is a lack of understanding of how each subunit interacts with each other. So far, theoretical studies of methyl group transfer were carried out for the structural models of the active site of each subunit. However, those studies do not include the effect of the enzymatic environment, which is crucial for a comprehensive understanding of enzyme-mediated methyl transfer reactions. Herein, to explore how two subunits interact with each other and how the methyl transfer reaction is catalyzed by MeTrs, molecular docking of the functional units of MetH and MtmBC was carried out. Along with the interactions of the functional units, the reaction coordinates, including the Co-C bond distance for methylation of cob(I)alamin (CoICbl) and the C-S bond distance in demethylation reaction of cob(III)alamin (CoIIICbl), were considered. The functional groups should be arranged so that there is an appropriate distance to transfer a methyl group and present results indicate that steric interactions can limit the number of potential arrangements. This calls into question the possibility of SN2-type mechanism previously proposed for MeTrs. Further, it leads to the conclusion that the methyl transfer reaction involves some spatial changes of modules suggesting an alternate radical-based pathway for MeTrs-mediated methyl transfer reactions. The calculations also showed that changes in torsion angles induce a change in reaction coordinates, namely Co-C and C-S bond distances, for the methylation and demethylation reactions catalyzed both by MetH and MtmBC.

Synthesis, characterization and cytotoxicity studies of Co(III)-flavonolato complexes.

Hypoxia activated Co(III) complexes as prodrugs may provide with a selective delivery of cytotoxic or antibacterial compounds. Whithin this field sixteen novel Co(III) ternary complexes with the general formula [Co(4N)(flav)](ClO4)2, where 4N = tris(2-aminoethyl)amine (tren) or tris(2-pyridylmethyl)amine (tpa) and flav = deprotonated form of differently substituted flavonols have been synthesized, characterized, and their cytotoxicity assayed under both normoxic and hypoxic conditions. Molecular structures of two free flavonols and seven complexes are also reported. In all the complexes the bioligands exhibited the expected (O,O) coordination mode and the complexes showed a slightly distorted octahedral geometry. Cyclic voltammetric studies revealed that both the substituents of the flavonoles and the type of 4N donor ligands had an impact on the reduction potential of the complex. The ones containing tren demonstrated significantly higher stability than the tpa analogues, making these former compounds promising candidates for the development of hypoxia-activated prodrug complexes. Tpa complexes showed higher activity against both selected human cancer cell lines (A549, A431) than their free ligand flavonols, indicating that the anticancer activity of the bioligand can be enhanced upon complexation. However, slight hypoxia-selectivity was found only for a tren complex (11) with moderate cytotoxicity.

Molecular Recognition of Imidazole Derivatives by Co(III)-Porphyrinsin Phosphate Buffer (pH = 7.4) and Cetylpyridinium Chloride Containing Solutions.

Bymeans of spectrophotometric titration and NMR spectroscopy, the selective binding ability ofthe Co(III)-5,15-bis-(3-hydroxyphenyl)-10,20-bis-(4-sulfophenyl)porphyrin (Со(III)Р1) andCo(III)-5,15-bis-(2-hydroxyphenyl)-10,20-bis-(4-sulfophenyl)porphyrin (Со(III)Р2) towards imidazole derivatives of various nature (imidazole (L1), metronidazole (L2), and histamine (L3)) in phosphate buffer (pH 7.4) has been studied. It was found that in the case of L2, L3 the binding of the "first" ligand molecule by porphyrinatesCo(III)P1 and Co(III)P2 occurs with the formation of complexes with two binding sites (donor-acceptor bond at the center and hydrogen bond at the periphery of the macrocycle), while the "second" ligand molecule is added to the metalloporphyrin only due to the formation of the donor-acceptor bond at the macrocycle coordination center. The formation of stable complexes with two binding sites has been confirmed by density functional theory method (DFT) quantum chemical calculations and two-dimensional NMR experiments. It was shown that among the studied porphyrinates, Co(III)P2 is more selective towards to L1-L3 ligands, and localization of cobalt porphyrinates in cetylpyridinium chloride (CPC) micelles does not prevent the studied imidazole derivatives reversible binding. The obtained materials can be used to develop effective receptors for recognition, delivery, and prolonged release of drug compounds to the sites of their functioning. Considering that cetylpyridinium chloride is a widely used cationic biocide as a disinfectant, the designed materials may also prove to be effective antimicrobial agents.