On similarity of hydrogen-bonded networks in liquid formamide and water as revealed in the static dielectric studies

The paper presents the experimental verification of the result obtained with the molecular dynamics simulation which revealed the differences in the topology of the hydrogen-bonded networks in liquid formamide and water, namely, the differences in their intermolecular cyclization process (I. Bakó, et al. J. Chem. Phys. 2010, 132, 014506). It is shown in our paper that the difference in the (simulated) size distribution of the hydrogen-bonded molecular rings in water (a relatively sharp maximum at about 6 molecules) and formamide (a broad maximum at about 11 molecules) strongly manifests itself in the experimental values of the Kirkwood correlation factor of the compounds. A much larger number of molecules included in the cyclic species (of more or less compensated dipole moment) leads to significant decrease of the Kirkwood correlation factor of formamide in comparison to that of water. Besides, as a consequence of an enhancement in formation of the cyclic multimers of formamide, one observes an essential reduction of the orientational entropy increment of that liquid, in comparison to the entropy effect related to liquid amides where the chain multimers are formed.     

The chemical composition of the essential oils of Cirsium palustre and C. rivulare and their antiproliferative effect

The composition of the essential oils of Cirsium palustre and C. rivulare and their antiproliferative activity against breast adenocarcinoma cells (MCF-7 and MDA-MBA-231) were investigated. The essential oils obtained by hydro-distillation from the roots (yield 0.2 and 0.1% v/w, respectively), leaves and inflorescences (yield below 0.01%), were analyzed by gas chromatography coupled with mass spectrometry (GC-MS). The composition of the essential oils in the respective organs of each plant differed considerably. On the other hand, similarities were observed in the composition of root and leaf oils. In C. palustre and C. rivulare root oil, 50 and 39 constituents were identified, accounting for 95.3% and 92.4% of the total content. The main components were aplotaxene and its derivatives, representing 78.6% and 46.6% of the total content. In leaf oils of both species, 59 and 49 compounds, respectively, were identified, representing 67.4% and 78.3% of the total content. The major constituents were beta-damascenone (4.1% and 13.4%, respectively) and beta-ionone (6.7% and 5.3%, respectively). Short-chain saturated and unsaturated aliphatic alcohols and aldehydes constituted another important group of compounds (17.7% and 9.0%, respectively). The essential oils of the roots have moderate anti-proliferative activity, with IC50 values ranging from 110 to 140 microg/mL. These concentrations were below the level able to inhibit the proliferation of healthy cells.     

Modelling relation between oxidation resistance and tribological properties of non-toxic lubricants with the use of artificial neural networks

The lubricants based on vegetable oils, as environmental friendly, are urgently sought. However, in addition to ecological characteristics, the lubricating properties have to be met. To meet these requirements the active additives influencing the lubricating properties and oxidation resistance are used. The useful lifetime of lubricants is determined largely by their abilities to resist oxidation. The article presented the results of new, ecological lubricants development. The oxidation performances of different developed lubricants have been tested. The experimentally determined oxidation stability of the compositions based on vegetable oils are presented. Analysed oxidation onset temperature was obtained from the differential scanning calorimetry (DSC) curves, which provides the rapid prediction of the oxidative stability of lubricants. Besides the lubricating composition based on vegetable oils, the developed greases-based mineral, or synthetic oil were investigated. The properties of these greases were evaluated using the measurement of parameters describing structure (penetration) and resistance to high temperature (dropping point). The lubricating properties of both the greases and vegetable oil compositions were tested on four-ball testing machine. In the results of the modelling of the lubricating properties the neural network models for the both types of the lubricants were developed. A discussion of the research results and analysis of models validity is given below. The experimental results are compared with the calculated using the neural models. An acceptable agreement was achieved.     

Thermal degradation of copolymers based on selected alkyl methacrylates

The thermal stability and thermal degradation of copolymers based on selected alkyl methacrylates at temperatures between 250 and 400?°C have been studied using pyrolysis?Cgas chromatography. The type and composition of thermal degradation products gave useful information about the mechanism of pyrolysis of copolymers synthesized by using typical commercially available alkyl methacrylates. It was observed that the main thermal degradation products from alkyl methacrylate copolymers are monomers of alkyl methacrylates using by synthesis. Other pyrolysis by-products formed during thermal degradation were carbon dioxide, carbon monoxide, methane, ethane, methanol, ethanol, and propanol-1.     

Azothia- and Azoxythiacrown Ethers as Ion Carriers. Part I. Cationic Response of Membrane Electrodes

13-Membered azothia- and azoxythiacrown ethers have been applied as ion carriers in ion-selective membrane electrodes. Their sensitivity and selectivity were studied towards alkali, alkaline earth, transition and heavy metal cations. It was found that membranes doped with the azoxythiacrown ether (A) show higher affinity towards Pb²⁺ than Cu²⁺ (log K_Cu,Pb ^pot = 1.7), whereas membranes with the azothiacrown ether (B) are more selective towards Cu²⁺ than Pb²⁺ (log K_Cu,Pb ^pot = -2.4). The discrimination of alkali and alkaline earth cations was found to be greater for B than for A. Electrodes with both ionophores suffered from strong interference by Ag⁺ and Hg²⁺. The relation between the carrier structure and electrode properties has been discussed.     

An unusual nicotinamide derivative, 4-pyridone-3-carboxamide ribonucleoside (4PYR), is a novel endothelial toxin and oncometabolite

Our recent studies identified a novel pathway of nicotinamide metabolism that involves 4-pyridone-3-carboxamide-1-β-D-ribonucleoside (4PYR) and demonstrated its endothelial cytotoxic effect. This study tested the effects of 4PYR and its metabolites in experimental models of breast cancer. Mice were divided into groups: 4T1 (injected with mammary 4T1 cancer cells), 4T1 + 4PYR (4PYR-treated 4T1 mice), and control, maintained for 2 or 21 days. Lung metastasis and endothelial function were analyzed together with blood nucleotides (including 4PYR), plasma amino acids, nicotinamide metabolites, and vascular ectoenzymes of nucleotide catabolism. 4PYR metabolism was also evaluated in cultured 4T1, MDA-MB-231, MCF-7, and T47D cells. An increase in blood 4PYR in 4T1 mice was observed at 2 days. 4PYR and its metabolites were noticed after 21 days in 4T1 only. Higher blood 4PYR was linked with more lung metastases in 4T1 + 4PYR vs. 4T1. Decreased L-arginine, higher asymmetric dimethyl-L-arginine, and higher vascular ecto-adenosine deaminase were observed in 4T1 + 4PYR vs. 4T1 and control. Vascular relaxation caused by flow-dependent endothelial activation in 4PYR-treated mice was significantly lower than in control. The permeability of 4PYR-treated endothelial cells was increased. Decreased nicotinamide but enhanced nicotinamide metabolites were noticed in 4T1 vs. control. Reduced N-methylnicotinamide and a further increase in Met2PY were observed in 4T1 + 4PYR vs. 4T1 and control. In cultured breast cancer cells, estrogen and progesterone receptor antagonists inhibited the production of 4PYR metabolites. 4PYR formation is accelerated in cancer and induces metabolic disturbances that may affect cancer progression and, especially, metastasis, probably through impaired endothelial homeostasis. 4PYR may be considered a new oncometabolite.Subject terms: Mechanisms of disease, Pathogenesis, Breast cancer     

Molecular Weight Distribution in Living Polymerization Proceeding with Reshuffling of Polymer Segments due to Chain Transfer to Polymer with Chain Scission, 2. Monte Carlo Simulation of Polymer Reshuffling Proceeding with Disproportionation of Chain Functionalities

The method for analyzing the reshuffling of polymer segments developed previously has been extended to systems involving the disproportionation of chain functionalities. The effect of interchain exchange reactions of this type, leading to the redistribution of chain lengths and of the chain functionalities (redistribution of living and dead chain ends), was analyzed by means of the Monte Carlo simulations. In the systems, in which no propagation occurs (monomer concentration equal to zero), a set of polymer chains containing one living and one dead end was taken as an initial material. A series of simulations were performed for systems with differing molecular weight distributions of the starting macromolecules. Uniform (no chain length distribution polymer – all chains are of the same length), Poisson, and the most probable (geometric) distributions were taken into consideration. Although the molecular weight distributions (MWDs) of functionally different chains of the same polymer were different apart from the eventual equilibrium conditions, the overall MWD was very close to that observed in analogous systems without disproportionation. The same was observed concerning MWDs in modeled polymerization systems, in which reshuffling and disproportionation accompanied propagation. Consequently, a method of estimating the ratio of rate constants of propagation and reshuffling (i. e. k_p /k _tr) in the relevant polymerization systems, using the observed polydispersity indexes, was proposed. The extent of disproportionation can be evaluated from the determined relationships of the polydispersity index and of the monofunctional chains fraction as functions of the average number of chain transformations.     

An attempt to simulate structure and realistic images of scratches on rough polymeric surfaces

Numerical simulation of scratching has been shown to exhibit many advantages in material development and surface design and can provide detailed information associated with the scratch structure. However, the visual appearance of simulated scratches in real-world scenarios has seldom been studied. This study simulates the structure and visual appearance of scratches on rough polymer surfaces by combining the finite element method (FEM) with computer imaging (CI) techniques. FEM modeling of scratching incorporates a wide range of microgeometries in rough surfaces to ensure that the resulting scratch surfaces contain all features, regardless of whether they are visible to the human eye. Computer graphics produce realistic images of numeric scratch surfaces in real-world lighting conditions. This method demonstrates the advantages of easily simulating scratches on rough surfaces and assessing both abrasion strength and visual scratch resistance. Scratch tests on commercial polymer surfaces at different scratch forces demonstrate that the method can satisfactorily predict the structures and scales of scratches. The simulated images correlate closely with camera-acquired photographs in terms of the visual appearance of scratch surfaces, effect of lighting conditions, and dependence of the visual width of scratches on the scratching force, material, pigment, and additive in the material.     

Effect of Cr(III) passivation layer on surface modifications of zinc-nickel coatings in chloride solutions

Surface chemical and morphological modifications of as-plated and Cr(III)-passivated monophasic zinc-nickel coatings induced by corrosion in chloride solutions are demonstrated. The passivated samples showed slower anodic dissolution, less significant de-alloying, smaller surface dezincification and lower coating cracking, as demonstrated by Scanning Electron Microscopy and Energy Dispersive X-ray Spectroscopy (SEM-EDX) of the surface and inductively coupled plasma atomic emission spectroscopy solution analysis. Surface characterization by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and SEM-EDS indicated simonkolleite as the main corrosion product for both, as-plated and Cr(III)-passivated coatings. In contrast, only for as-plated coating, which experienced higher cracking, new Ni containing phases (metallic Ni and NiO) were evidenced. The phase transition via selective dissolution of zinc is supposed to increase the concentration of the structural defects and could explain cracking in the non-passivated Zn-Ni coating.