New heterometallic Co/Zn, Ag/Co, and Ag/Zn imidazolates: structural characterization and catalytic activity in the oxidation of organic compounds.

Nanocrystalline powders of monometallic and bimetallic imidazolates of Co, Zn and Ag were produced by a reaction carried out in water. The powders were characterized by powder X-ray diffraction and the crystal structures of the new compounds Ag2ZnIm4 and Ag2CoIm4 (Im = imidazolate) were solved. Heterometallic Co/Zn imidazolates showed the known Zn-zni crystal structure while Ag/Zn and Ag/Co systems were isostructural to the copper analogs. The powders were further characterized by EDX, UV-Vis and FTIR ATR spectroscopy in the solid state. The catalytic experiments indicated that out of the studied heterometallic compounds only Ag2Co(Im)4 exhibits some catalytic activity in the oxidation reaction of 1-phenylethanol with tert-butylhydroperoxide at elevated temperatures.

Reactions of cobalt(ii) chloride and cobalt(ii) acetate with hemisalen-type ligands: ligand transformation, oxidation of cobalt and complex formation. Preliminary study on the cytotoxicity of Co(ii) and Co(iii) hemisalen complexes.

Several molecular cobalt(ii) complexes, one Co(ii) coordination polymer and one ionic cobalt(iii) complex with imine hemisalen ligands were synthesized. The hemisalen ligands were synthesized from o-vanillin (oVP) and diverse aminopyridines (compounds HL1-HL4) or aminophenol (compound HL5). It was observed that cobalt(ii) chloride in dry acetonitrile catalyzes a transformation of HL1 and HL3 instead of complex formation. The conversion of these imines proceeded via self-cyclization to N-2''-pyridyl-2,6-dioxo-9-aza-[c,g]di-2'-methoxybenzo nonan or its methyl derivative as the major product. The remaining reactions were performed using imines HL1-HL5 and cobalt(ii) acetate Co(Ac)2 in methanol or DMSO/acetonitrile resulting in forming a series of cobalt complexes. The following series of compounds was obtained: two similar tetrahedral molecular Co(ii) complexes [Co(L1)2] and [Co(L3)2], one trinuclear, mixed-ligand Co3(Ac)2(L4)2(oVP)2, one coordination polymer {Co(L2)2}∞ and finally one octahedral anionic Co(iii) complex [HNEt3][Co(L5)3]. The latter complex formed in a cobalt(ii) acetate reaction with a hemisalen HL5 derived from oVP and 2-aminophenol. The molecular structures of all compounds were confirmed by X-ray diffraction, and the cytotoxicity of Co(ii) and Co(iii) complexes towards cancer cell lines HCT116, HL-60 and normal cell line MRC-5 was studied.

Tailoring Diffusional Fields in Zwitterion/Dopamine Copolymer Electropolymerized at Carbon Nanowalls for Sensitive Recognition of Neurotransmitters.

The importance of neurotransmitter sensing in the diagnosis and treatment of many psychological illnesses and neurodegenerative diseases is non-negotiable. For electrochemical sensors to become widespread and accurate, a long journey must be undertaken for each device, from understanding the materials at the molecular level to real applications in biological fluids. We report a modification of diamondized boron-doped carbon nanowalls (BCNWs) with an electropolymerized polydopamine/polyzwitterion (PDA|PZ) coating revealing tunable mechanical and electrochemical properties. Zwitterions are codeposited with PDA and noncovalently incorporated into a structure. This approach causes a specific separation of the diffusion fields generated by each nanowall during electrochemical reactions, thus increasing the contribution of the steady-state currents in the amperometric response. This phenomenon has a profound effect on the sensing properties, leading to a 4-fold enhancement of the sensitivity (3.1 to 14.3 µA cm-2 µM-1) and a 5-fold decrease of the limit of detection (505 to 89 nM) in comparison to the pristine BCNWs. Moreover, as a result of the antifouling capabilities of the incorporated zwitterions, this enhancement is preserved in bovine serum albumin (BSA) with a high protein concentration. The presence of zwitterion facilitates the transport of dopamine in the direction of the electrode by intermolecular interactions such as cation-π and hydrogen bonds. On the other hand, polydopamine units attached to the surface form molecular pockets driven by hydrogen bonds and π-π interactions. As a result, the intermediate state of dopamine-analyte oxidation is stabilized, leading to the enhancement of the sensing properties.

Simple synthesis route for fabrication of protective photo-crosslinked poly(zwitterionic) membranes for application in non-enzymatic glucose sensing.

This work focuses on the fabrication of non-enzymatic glucose sensing materials based on laser-formed Au nanoparticles embedded in Ti-textured substrates. Those materials possess good catalytic activity toward glucose oxidation in 0.1 × phosphate buffered saline as well as resistance to some interferants, such as ascorbic acid, urea, and glycine. The electrodes are further coated with three different polymers, that is, Nafion, photo-crosslinked poly(zwitterions) based on sulfobetaine methacrylate, and a hybrid membrane consisting of both polymers. Both the optimal integrity of the material and its catalytic activity toward glucose oxidation were maintained by the hybrid membranes with a large excess of poly(zwitterions) (mass ratio 20:1). The chemical structures of the as-formed membranes are confirmed by Fourier transform infrared spectroscopy. Due to the zwitterionic nature of the coating, the electrodes are resistant to biofouling and maintain electrochemical activity toward glucose for 4 days. Moreover, due to the synergistic effect of both Nafion and poly(zwitterions), the interference from the two compounds, namely, from acetylsalicylic acid and acetaminophen, was diminished. Besides the presence of polymer membranes, the electrode possesses a sensitivity of 36.8 µA cm-2  mM-1 in the linear range of 0.4-12 mM, while the limit of detection was estimated to be 23 µM. Finally, the electrodes are stable, and their response is not altered even by 1,000 bending cycles.

Novel 1,2,3-Triazole Derivatives as Mimics of Steroidal System-Synthesis, Crystal Structures Determination, Hirshfeld Surfaces Analysis and Molecular Docking.

Herein, we present the synthesis and crystal structures determination of five 4-(1-phenyl-1H-1,2,3-triazol-4-yl)phenol derivatives containing halogen atoms, 6a-e, which may be used as an excellent mimic of steroids in the drug development process. Good quality crystals obtained for all of the synthesized compounds allowed the analysis of their molecular structures. Subsequently, the determined crystal structures were used to calculate the Hirshfeld surfaces for each of the synthesized compounds. Furthermore, results of our docking studies indicated that synthesized derivatives are able to bind effectively to the active sites of selected enzymes and receptors involved in the hormone biosynthesis and signaling pathways, analogously to the native steroids.

Solvothermal synthesis and structural characterization of three polyoxotitanium-organic acid clusters.

Three new titanium oxo-clusters Ti4O2(OiPr)10(OOCPhMe)2 (I), Ti6O4(OEt)8(OOCPhMe)8 (II) and Ti6O6(OEt)6(OOCCHPh2)6 (III) were obtained by easy one-step solvothermal reactions of titanium(iv) isopropoxide, alcohols and carboxylic acids. The three compounds were characterized by single-crystal and powder X-ray diffraction, TGA/DSC, optical and electron microscopy, and FTIR and NMR spectroscopy. X-ray powder diffraction and spectroscopy confirmed the purity of the compounds. Structural analysis indicates that in all compounds the titanium(iv) ions are six-coordinated (distorted octahedra). (I) is a tetranuclear complex containing a Ti4(µ4-O)(µ2-O) core, which is linked by two (µ2-OOCPhMe), four (µ2-OiPr) and six OiPr ligands. (II) and (III) are hexanuclear complexes with different cores, respectively Ti6(µ3-O)2(µ2-O)2 and Ti6(µ3-O)6. The coordination sphere of the Ti atoms is filled by eight (µ2-OOCPhMe), two (µ2-OEt) and six OEt in (II) and six (µ2-OOCHPh2) and six OEt in (III). Different steric hindrance of substituents attached to the carboxyl group or different concentrations lead to three main different cluster geometries with two ligands. The tetranuclear and the hexanuclear clusters were obtained with the OOCPhMe ligand, while the hexagonal prism cluster was obtained with the OOCCHPh2 ligand. Hirshfeld surface calculations indicated that the packing is driven by C-O⋯H-C weak hydrogen bonds. The clusters can be used as molecular models of organic molecules bonded to titania surface, used in organic photovoltaic (dye sensitized solar cells) or other optoelectronic applications.

Atmospheric deposition of microplastics in the coastal zone: Characteristics and relationship with meteorological factors.

In this study, the quantitative and qualitative compositions of microplastics (MPs) deposited from the atmosphere in the coastal zone were analysed. Moreover, links between MP deposition and meteorological factors (air humidity, wind speed, precipitation height, and air mass trajectories) were investigated. MP deposition samples were collected in the southern Baltic area in 2017 and 2018 for 286 days in total. The morphological features of MPs (shape and size) were analysed using a digital microscope. Qualitative analysis was performed using micro-attenuated total reflectance Fourier-transform infrared spectroscopy (µATR FT-IR). The size of the deposited MPs ranged from 5 µm to 5000 µm, and smaller size classes (<720 µm) were predominant (70%). Fibres were of the dominant type (60%). Films and fragments constituted 26% and 14% of the total MPs, respectively, while 55% of the MPs found in the study were polymers often used in textiles, packaging materials, and fishing gear (polyesters and polypropylene). The atmospheric MP deposition ranged from 0 m-2·d-1 to 30 m-2·d-1 (average: 10 ± 8 m-2·d-1; median: 8 m-2·d-1). Based on the air mass trajectory cluster analysis, MPs deposited in Gdynia mainly originated from local sources (<100 km). Furthermore, higher MP deposition occurred when the inflowing air masses were terrestrial, and lower deposition occurred when they were marine. On average, during wet periods twice the amount of MPs was deposited in comparison with dry periods. During dry periods deposition increased with increasing wind speed and was intensified by high relative humidity.

Novel approach to interference analysis of glucose sensing materials coated with Nafion.

We focus here on a novel approach to analysing the mechanisms of interference phenomena in glucose sensing, taking into account the changes within the Nafion layer deposited on the active surface. Several electrochemical techniques were used to verify the sustainability of catalytic properties of the electrode material after exposure to different compounds, i.e. ascorbic acid (AA), glycine, urea, acetylsalicylic acid (AsA), and acetaminophen (AAp). Through analysis of impedance data, we concluded that AAp and AsA were trapped permanently in the Nafion membrane, which significantly affected results repeatability. These observations were also confirmed by FT-IR investigations of the membrane after its immersion in solutions containing different interfering species. Moreover, after exposure to AsA and, unexpectedly, large concentrations of urea, the catalytic properties were completely lost, which, in consequence, make sensor reuse impossible. Such behaviour was justified by the chain reorganisation and swelling. Mechanisms involving adsorption onto the interphase and absorption in the membrane were proposed as key factors responsible for deterioration of membrane functionality and were confronted with FT-IR investigations. Following that, application of Nafion for non-invasive glucose sensor protection is unsatisfactory and cannot be considered for multiple detection procedures, especially taking into account biological fluids full of different interfering species.

Crystal structures of (E)-3-(4-hy-droxy-benzyl-idene)chroman-4-one and (E)-3-(3-hy-droxy-benzyl-idene)-2-phenyl-chroman-4-one.

The synthesis and crystal structures of (E)-3-(4-hy-droxy-benzyl-idene)chroman-4-one, C16H12O3, I, and (E)-3-(3-hy-droxy-benzyl-idene)-2-phenyl-chroman-4-one, C22H16O3, II, are reported. These compounds are of inter-est with respect to biological activity. Both structures display inter-molecular C-H⋯O and O-H⋯O hydrogen bonding, forming layers in the crystal lattice. The crystal structure of compound I is consolidated by π-π inter-actions. The lipophilicity (logP) was determined as it is one of the parameters qualifying compounds as potential drugs. The logP value for compound I is associated with a larger contribution of C⋯H inter-action in the Hirshfeld surface.

A Cu/Zn heterometallic complex with solvent-binding cavity, catalytic activity for the oxidation of 1-phenylethanol and unusual magnetic properties.

Mononuclear and polymeric complexes of zinc(ii) and copper(ii) have been synthesized using two isomers of the hemi-salen ligand with a different mutual orientation of donor atoms. The heterometallic Cu/Zn metallocycle features a catalytic niche filled with the molecule of water and molecules of methanol. This unusual compound exhibits both pronounced catalytic activity in the reaction of oxidation of a secondary alcohol to ketone and field induced slow magnetic relaxation, which is a very rare phenomenon among Cu(ii) complexes.

Anticancer and antimicrobial properties of novel η6-p-cymene ruthenium(ii) complexes containing a N,S-type ligand, their structural and theoretical characterization.

Ruthenium(ii) complexes are lately of great scientific interest due to their chemotherapeutic potential as anticancer and antimicrobial agents. Here we present the synthesis of new pyrazole carbothioamide derivatives and their four arene-ruthenium complexes. The title compounds were characterized with the application of IR, NMR, mass spectrometry, elemental analysis and X-ray diffraction. Additionally, for new complexes DFT calculations were done. Their antimicrobial activity (MIC, MBC/MFC) was examined in vitro against Staphylococcus aureus, Staphylococcus epidermidis, Enterococcus faecalis, Pseudomonas aeruginosa, Proteus vulgaris and Candida albicans. Their cytotoxic effects, using the MTT assay, against three cancer cell lines: HL-60, NALM-6, WM-115 and normal human foreskin fibroblasts (HFF-1) were also investigated. The influence of the new arene-ruthenium(ii) complexes on the DNA structure was also tested. From our results, compound 2d showed higher cytotoxicity against melanoma cell line WM-115 than cisplatin. Strong biostatic and biocidal activity of the tested complexes against Gram-positive bacteria, including S. aureus, S. epidermidis and E. faecalis was demonstrated. The new arene-ruthenium(ii) compounds could not only inhibit proliferation of cancer cells, but also protect patients against malignant wound infections.

Modeling and MANOVA studies on toxicity and endocrine potential of packaging materials exposed to different extraction schemes.

The stability of the linings of packaging that is in contact with the goods stored has been of major concern during decades of the development of packaging materials. In this work, an attempt was undertaken to assess the applicability of using two bioassays (Microtox® and XenoScreen YES/YAS) in estimating the stability of packaging (cans, caps, multilayer material) and the impact of their degradation on the toxicity of some simulated media. The assessment of the impact of packaging storage conditions (temperature, disinfection, preservation, extracting and washing solvents) was planned and performed with i) regression modeling of the experimental effects on the ecotoxicity readings, ii) ANOVA and MANOVA estimation of the experimental conditions as significant factors affecting the toxicity results and iii) FTIR analysis of the packages. It is shown that the effects of temperature and extraction solvents could be quantitatively assessed by the agreement between all methods applied. It can be stated that temperature and acidity as well as the alcohol content in the sensitive media have the greatest impact on the toxicity of the extract and thus on the stability of the internal lining and the extractability of xenobiotics.

Silver complexes stabilized by large silanethiolate ligands - crystal structures and luminescence properties.

Bulky silanethiolate and disiladithiolate ligands were applied to synthesize one mononuclear and three trinuclear silver complexes including two cyclic "microclusters" and a linear tri-nuclear silanethiolate complex. All obtained compounds are characterized by X-ray diffraction and FT-IR. NMR and emission spectroscopies were used where possible. The first trinuclear anionic silver thiolate is structurally characterized. The influence of the different charge of cyclic silver complexes as well as the overall ligand environment on the structural properties is demonstrated. The impact of the different synthetic routes on the final structures of the obtained clusters - cyclic or linear - is discussed.

Sources and fate of microplastics in marine and beach sediments of the Southern Baltic Sea-a preliminary study.

Microplastics' (particles size ≤5 mm) sources and fate in marine bottom and beach sediments of the brackish are strongly polluted Baltic Sea have been investigated. Microplastics were extracted using sodium chloride (1.2 g cm-3). Their qualitative identification was conducted using micro-Fourier-transform infrared spectroscopy (µFT-IR). Concentration of microplastics varied from 25 particles kg-1 d.w. at the open sea beach to 53 particles kg-1 d.w. at beaches of strongly urbanized bay. In bottom sediments, microplastics concentration was visibly lower compared to beach sediments (0-27 particles kg-1 d.w.) and decreased from the shore to the open, deep-sea regions. The most frequent microplastics dimensions ranged from 0.1 to 2.0 mm, and transparent fibers were predominant. Polyester, which is a popular fabrics component, was the most common type of microplastic in both marine bottom (50%) and beach sediments (27%). Additionally, poly(vinyl acetate) used in shipbuilding as well as poly(ethylene-propylene) used for packaging were numerous in marine bottom (25% of all polymers) and beach sediments (18% of all polymers). Polymer density seems to be an important factor influencing microplastics circulation. Low density plastic debris probably recirculates between beach sediments and seawater in a greater extent than higher density debris. Therefore, their deposition is potentially limited and physical degradation is favored. Consequently, low density microplastics concentration may be underestimated using current methods due to too small size of the debris. This influences also the findings of qualitative research of microplastics which provide the basis for conclusions about the sources of microplastics in the marine environment.

Variable-temperature X-ray diffraction study of structural parameters of NH---S hydrogen bonds in triethylammonium and pyridinium silanethiolates.

Two hydrogen-bonded, well defined compounds were synthesized from tris(2,6-diisopropyl)phenoxysilanethiol (TDST) and triethylamine (TDST-TEA) or pyridine (TDST-py). The crystalline compounds were characterized in the solid state by variable-temperature X-ray diffraction measurements and ATR FT-IR spectroscopy. The toluene solutions of TDST-TEA and TDST-py were studied by NMR spectroscopy. The total hydrogen-bond energies and FT-IR spectra were calculated with the use of BLYP-D/TZP and B3LYP/6-31G(d,p)/GD3BJ methods. Thermochemical parameters and potential energy scans were calculated at the B3LYP/6-31G(d,p)/GD3BJ level. All results point to the higher energy of bonding in TDST-TEA both in the solid state and in solution. At the same time the potential energy scan reveals a very broad double-well hydrogen bond in TDST-py, indicating good stabilization of the system for a wide range of D-H...A distances.

Structural Variety of Cobalt(II), Nickel(II), Zinc(II), and Cadmium(II) Complexes with 4,4'-Azopyridine: Synthesis, Structure and Luminescence Properties.

Self-assembled bi- and polymetallic complexes of Co(II), Ni(II), Zn(II), and Cd(II) were obtained by the reaction of 4,4'-azopyridine (azpy) with metal tri-tert-butoxysilanethiolates (Co, 1; Cd, 2), acetylacetonates (Ni, 3; Zn, 4), and acetates (Cd, 5). All compounds were characterized by single-crystal X-ray structure analysis, elemental analysis, FTIR spectroscopy, and thermogravimetry. Complexes 1, 2 and 4, 5 exhibit diverse structural conformations: 1 is bimetallic, 2 and 4 are 1D coordination polymers, and 5 is a 2D coordination framework formed from bimetallic units. The obtained complexes contain metal atoms bridged by a molecule of azpy. The luminescent properties of 1-5 were investigated in the solid state.

Synthesis and characterization of mononuclear Zn(II), Co(II) and Ni(II) complexes containing a sterically demanding silanethiolate ligand derived from tris(2,6-diisopropylphenoxy)silanethiol.

Four heteroleptic complexes of nickel(ii), cobalt(ii) and zinc(ii), containing a monodentate silanethiolate ligand derived from tris(2,6-diisopropylphenoxy)silanethiol (TDST), were prepared and characterized. Nickel(ii) and cobalt(ii) complexes of the formula M(NH3)2(TDST)2 (M = Ni(ii) complex , M = Co(ii) complex ) were obtained from the respective chlorides. Zinc complexes of the general formula Zn(acac)(TDST)(L), where L = EtOH (complex ) or H2O (complex ), were obtained from zinc acetylacetonate. A single-crystal X-ray structural analysis revealed that all crystalline products are solvent adducts. The geometries of ligands in the complexes are typical: distorted tetrahedral in zinc and cobalt(ii) complexes and square planar in nickel(ii) compounds. Magnetic studies performed for Ni(ii) and Co(ii) compounds confirmed the diamagnetic character of the first complex and high-spin paramagnetic configuration of the latter. Nickel(ii) and cobalt(ii) complexes were additionally characterized by UV-Vis and IR spectroscopy. IR bands for ligands in the complexes were assigned with the help of the DFT vibrational frequency calculations.

Intramolecular interactions in crystals of tris(2,6-diisopropylphenoxy)silanethiol and its sodium salts.

Hydrolytically stable silanethiol tris(2,6-diisopropylphenoxy)silanethiol (TDST) has been synthesized and reacted with sodium metal. In solid state TDST exhibits π-interactions between the S-H unit and the π-system of the arene, replaced by cation-π interactions in its sodium salts. The interactions are documented by crystal structures and FT-IR spectroscopy.

(1H-Pyrazole-κN)bis-(tri-tert-but-oxy-silane-thiol-ato-κ(2) O,S)cadmium.

The Cd(II) atom in the title complex, [Cd(C12H27O3SSi)2(C3H4N2)], is penta-coordinated by two O and two S atoms from the O,S-chelating silane-thiol-ate residue and one pyrazole N atom in a distorted geometry that is slightly closer to trigonal-bipyramidal than to square-based pyramidal. The pyrazole ligand is stabilized within the complex by an intra-molecular N-H⋯O hydrogen bond. One of the tert-butyl groups is disordered over two orientations with occupancy ratio of 0.534 (6):0.466 (6).

Bromidotetra-kis-(2-ethyl-1H-imidazole-κN (3))copper(II) bromide.

The Cu(II) ion in the title mol-ecular salt, [CuBr(C5H8N2)4]Br, is coordinated in a square-pyramidal geometry by four N atoms of imidazole ligands and one bromide anion in the apical position. In the crystal, the ions are linked by N-H⋯Br hydrogen bonds involving both the coordinating and the free bromide species as acceptors. A C-H⋯Br inter-action is also observed. Overall, a three-dimensional network results.