A Series of Novel 3D Coordination Polymers Based on the Quinoline-2,4-dicarboxylate Building Block and Lanthanide(III) Ions-Temperature Dependence Investigations.

A series of novel 3D coordination polymers [Ln2(Qdca)3(H2O)x]·yH2O (x = 3 or 4, y = 0-4) assembled from selected lanthanide ions (Ln(III) = Nd, Eu, Tb, and Er) and a non-explored quinoline-2,4-dicarboxylate building block (Qdca2- = C11H5NO42-) were prepared under hydrothermal conditions at temperatures of 100, 120, and 150 °C. Generally, an increase in synthesis temperature resulted in structural transformations and the formation of more hydrated compounds. The metal complexes were characterized by elemental analysis, single-crystal and powder X-ray diffraction methods, thermal analysis (TG-DSC), ATR/FTIR, UV/Vis, and luminescence spectroscopy. The structural variety of three-dimensional coordination polymers can be ascribed to the temperature effect, which enforces the diversity of quinoline-2,4-dicarboxylate ligand denticity and conformation. The Qdca2- ligand only behaves as a bridging or bridging-chelating building block binding two to five metal centers with seven different coordination modes arising mainly from different carboxylate group coordination types. The presence of water molecules in the structures of complexes is crucial for their stability. The removal of both coordinated and non-coordinated water molecules leads to the disintegration and combustion of metal-organic frameworks to the appropriate lanthanide oxides. The luminescence features of complexes, quantum yield, and luminescent lifetimes were measured and analyzed. Only the Eu complexes show emission in the VIS region, whereas Nd and Er complexes emit in the NIR range. The luminescence properties of complexes were correlated with the crystal structures of the investigated complexes.

Solvent influence on the crystal structures of new cadmium tri-tert-butoxysilanethiolate complexes with 1,4-bis(3-aminopropyl)piperazine: luminescence and antifungal activity.

Monocrystals of dinuclear µ-1,4-bis(3-aminopropyl)piperazine-κ4N1,N1':N4,N4'-bis[bis(tri-tert-butoxysilanethiolato-κS)cadmium(II)], [Cd2(C12H27O3SSi)4(C10H24N4)] or [Cd2{SSi(OtBu)3}4(µ-BAPP)], 1, and polynuclear catena-poly[[bis(tri-tert-butoxysilanethiolato-κS)cadmium(II)]-µ-1,4-bis(3-aminopropyl)piperazine-κ2N1':N4'], [Cd(C12H27O3SSi)2(C10H24N4)]n or [Cd{SSi(OtBu)3}2(µ-BAPP)]n, 2, with 1,4-bis(3-aminopropyl)piperazine (BAPP) and tri-tert-butoxysilanethiolate ligands, were obtained from the same ratio of reactants, but with different solvents used for the crystallization processes. The structures and properties of both complexes were characterized using elemental analysis, X-ray diffraction and FT-IR, 1H NMR and luminescence spectroscopy. Applied density functional theory (DFT) computational methods and noncovalent interaction (NCI) analysis were used for geometry optimization and visualization of the interactions between the metallic centres and their surroundings. The X-ray analysis revealed four-coordinate CdII centres bound to two S atoms of the silanethiolate groups and two N atoms of the BAPP ligand; however, it chelates to tertiary and primary N atoms in 1, whilst in 2 it does not chelate and bonds only to RNH2. The photoluminescence properties of complexes 1 and 2 result from free-ligand emission and differ significantly from each other with respect to emission intensity. Additionally, antifungal activity was investigated against 18 isolates of fungi. Compound 1 strongly inhibited the growth of three dermatophytes: Epidermophyton floccosum, Microsporum canis and Trichophyton rubrum.

Pyrolysis of Pruning Residues from Various Types of Orchards and Pretreatment for Energetic Use of Biochar.

The routine pruning and cutting of fruit trees provides a considerable amount of biowaste each year. This lignocellulosic biomass, mainly in the form of branches, trunks, rootstocks, and leaves, is a potential high-quality fuel, yet often is treated as waste. The results of a feasibility study on biochar production by pyrolysis of residues from orchard pruning were presented. Three types of biomass waste were selected as raw materials and were obtained from the most common fruit trees in Poland: apple (AP), pear (PR), and plum (PL) tree prunings. Two heating rates and three final pyrolysis temperatures were applied. For the slow (SP) and fast pyrolysis (FP) processes, the heating rates were 15 °C/min and 100 °C/min, respectively. The samples were heated from 25 °C up to 400, 500, and 600 °C. Chemical analyses of the raw materials were conducted, and the pyrolysis product yields were determined. A significant rise of higher heating value (HHV) was observed for the solid pyrolysis products, from approximately 23.45 MJ/kg for raw materials up to approximately 29.52 MJ/kg for pyrolysis products at 400 °C, and 30.53 MJ/kg for pyrolysis products at 600 °C. Higher carbon content was observed for materials obtained by fast pyrolysis conducted at higher temperatures.

Insights into the Thermo-Mechanical Treatment of Brewers' Spent Grain as a Potential Filler for Polymer Composites.

This paper investigated the impact of twin-screw extrusion parameters on the properties of brewers' spent grain. The chemical structure, antioxidant activity, particle size, and color properties, as well as the emission of volatile organic compounds during extrusion, were investigated. The main compounds detected in the air during modifications were terpenes and terpenoids, such as α-pinene, camphene, 3-carene, limonene, or terpinene. They could be considered as a potential threat to human health and the environment. Changes in the chemical structure, antioxidant activity, and color of materials after modification indicated the Maillard reactions during extrusion, which resulted in the generation of melanoidins, especially at higher temperatures. This should be considered an exciting feature of this treatment method because modified brewers' spent grain may improve the thermooxidative stability of polymer materials. Moreover, the impact of the brewers' spent grain particle size on color and browning index used to determine the melanoidins content was investigated. The presented results show that proper adjustment of extrusion parameters enables the preparation of brewers' spent grain with the desired appearance and chemical properties, which could maximize the efficiency of the modification process.

Novel tetrahedral cobalt(ii) silanethiolates: structures and magnetism.

Three heteroleptic complexes of Co(ii) tri-tert-butoxysilanethiolates have been synthesized with piperidine [Co{SSi(OtBu)3}2(ppd)2] 1, piperazine [Co{SSi(OtBu)3}2(NH3)]2(µ-ppz)·2CH3CN 2, and N-ethylimidazole [Co{SSi(OtBu)3}2(etim)2] 3. The complexes have been characterized by a single-crystal X-ray, revealing their tetrahedral geometry on Co(ii) coordinated by two nitrogen and two sulfur atoms. Complexes 1 and 3 are mononuclear, whereas 2 is binuclear. The spectral properties and thermal properties of 1-3 complexes were established by FTIR spectroscopy for solid samples and TGA. The magnetic properties of complexes 1, 2, and 3 have been investigated by static magnetic measurements and X-band EPR spectroscopy. These studies have shown that 1 and 3, regardless of the similarity in structure of CoN2S2 cores, demonstrate different types of local magnetic anisotropy. Magnetic investigations of 2 reveal the presence of weak antiferromagnetic intra-molecular Co(ii)-Co(ii) interactions that are strongly influenced by the local magnetic anisotropy of individual Co(ii) ions.

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.

Two isomorphous ZnII/CoII complexes with tri-tert-butoxysilanethiol and histamine, and (4-hydroxymethyl-1H-imidazole-kappaN)bis(tri-tert-butoxysilanethiolato-kappa2O,S)zinc(II).

The complexes [2-(1H-imidazol-4-yl-kappaN(3))ethylamine-kappaN]bis(tri-tert-butoxysilanethiolato-kappaS)cobalt(II), [Co(C(12)H(27)O(3)SSi)(2)(C(5)H(9)N(3))], and [2-(1H-imidazol-4-yl-kappaN(3))ethylamine-kappaN]bis(tri-tert-butoxysilanethiolato-kappaS)zinc(II), [Zn(C(12)H(27)O(3)SSi)(2)(C(5)H(9)N(3))], are isomorphous. The central Zn(II)/Co(II) ions are surrounded by two S atoms from the tri-tert-butoxysilanethiolate ligand and by two N atoms from the chelating histamine ligand in a distorted tetrahedral geometry, with two intramolecular N-H...O hydrogen-bonding interactions between the histamine NH(2) groups and tert-butoxy O atoms. Molecules of the complexes are joined into dimers via two intermolecular bifurcated N-H...(S,O) hydrogen bonds. The Zn(II) atom in [(1H-imidazol-4-yl-kappaN(3))methanol]bis(tri-tert-butoxysilanethiolato-kappa(2)O,S)zinc(II), [Zn(C(12)H(27)O(3)SSi)(2)(C(4)H(6)N(2)O)], is five-coordinated by two O and two S atoms from the O,S-chelating silanethiolate ligand and by one N atom from (1H-imidazol-4-yl)methanol; the hydroxy group forms an intramolecular hydrogen bond with sulfur. Molecules of this complex pack as zigzag chains linked by N-H...O hydrogen bonds. These structures provide reference details for cysteine- and histidine-ligated metal centers in proteins.

Inhibition of aldose reductase prevents lipopolysaccharide-induced inflammatory response in human lens epithelial cells.

PURPOSE: Bacterial infections are one of the major causes of human eye disease. Because the bacterial endotoxin lipopolysaccharide (LPS) is known to cause cytotoxicity through oxidative stress and an earlier study has shown that aldose reductase (AR) mediates oxidative stress signals, the purpose of this study was to investigate the anti-inflammatory effects of AR inhibition on LPS-induced activation of NF-kappaB-dependent signals in human lens epithelial cells (HLECs). METHODS: Growth-arrested HLECs were cultured without or with AR inhibitors or transfected with an AR small interfering (si)RNA. Subsequently, the cells were stimulated with LPS (1-10 mug/mL) for 24 hours. The cell viability was assessed by cell counts and MTT assay, and apoptosis was measured by nucleosomal degradation. Electrophoretic mobility gel shift assays were performed to determine the activation of NF-kappaB and AP1. The levels of nitric oxide, MMP-2, MMP-9, Cox-2, and TNF-alpha were measured by using specific ELISA kits. Western blot analysis was performed to determine the cleavage of poly(ADP-ribose) polymerase (PARP) and the activation of PKC and mitogen-activated protein kinase (MAPK). RESULTS: Bacterial LPS caused apoptosis of HLECs. Inhibition of AR by two structurally unrelated inhibitors, sorbinil and tolrestat, or ablation by AR siRNA prevented the LPS-induced apoptosis, activation of caspase-3 and cleavage of PARP protein. Inhibition of AR in HLECs also prevented the LPS-induced activation of redox-sensitive transcription factors such as NF-kappaB and AP1 and their downstream signals that lead to expression of Cox-2, MMP-2, MMP-9, and TNF-alpha proteins. In addition, inhibition of AR prevented LPS-induced activation of protein kinases upstream to NF-kappaB activation such as PKC and MAPK in HLECs. CONCLUSIONS: The results indicate that AR mediates the bacterial endotoxin signaling that could damage HLECs by regulating the signals that activate the redox-sensitive transcription factor NF-kappaB and cause inflammation. Thus, inhibition of AR could be a therapeutic target for Gram-negative bacterial infection-induced visual complications.

Aldose reductase prevents aldehyde toxicity in cultured human lens epithelial cells.

Aldehydes are widespread environmental and industrial compounds, which cause cytotoxicity, tissue damage, mutagenicity, and carcinogenicity leading to various disease conditions such as cardiovascular, bronchial, and visual complications. We have shown earlier that aldose reductase (AR) besides reducing glucose to sorbitol, efficiently reduces various toxic lipid-derived aldehydes, generated under oxidative stress, with K(m) in the physiological range. We have identified the role of AR in the prevention of various lipid aldehyde-induced cytotoxic signals leading to apoptosis in human lens epithelial cells (HLEC). HLEC were cultured without or with AR inhibitors followed by addition of various saturated and unsaturated lipid aldehydes with a carbon chain length varying from C3 to C10. The cell viability was assessed by cell counts and MTT assay, and apoptosis was measured by evaluating nucleosomal degradation and caspase-3 activation using specific ELISA kits. Although all the aldehydes caused apoptosis of HLEC, the unsaturated aldehydes were more toxic than saturated aldehydes. Inhibition of AR by sorbinil potentiated while the over-expression of AR prevented the apoptosis induced by various lipid aldehydes. AR over-expression also prevented the lipid aldehyde-induced activation of caspase-3, MAPK, JNK and the expression of Bcl-2 family of proteins in HLEC. The results indicate that the lipid aldehydes generated under oxidative stress are cytotoxic to HLEC leading to apoptosis and that the reduction of lipid aldehydes by AR would prevent it.