The Influence of Structural Parameters on the Reactivity of Model Complexes for Compound II: A Mini Review

The present brief review aims at elucidation of the parameters affecting the properties and reactivity of high valent iron(IV) oxo porphyrin complexes, being models of compound II reactive intermediate known from biochemistry of cytochromes and peroxidases. The stress is put on the influence of the axial ligand and porphyrin ring substituents, with special attention on implications for their catalytic activity.     

2-azaallylic rearrangement in homogeneous systems

In this work we present mechanism of the base-catalyzed 2-azaallylic rearrangement in homogeneous media. Detailed 2-azaallylic rearrangement studies have shown that tautomerism of derivatives of benzylidenebenzhydrylamines and N-fluorenylidenebenzylamines is not adequately encomposed by the Hammet equation and the equilibrium constant in the case of studied derivatives depends on the electronic as well as steric factors of the azaallylic system substituents. The presence of steric interactions which influence the equilibrium state has been additionally confirmed by means of crystallographic and molecular mechanics data as well as NOE studies. This revised version was published online in August 2006 with corrections to the Cover Date.     

N‐Oligo(3‐hydroxybutyrate)‐functionalized polypyrroles: towards bio‐erodible conducting copolymers

New copolymer materials have been prepared by chemical grafting of oligomeric 3‐hydroxybutyric acid (OHB) onto polypyrrole (PPy) derivatives. The influence of grafting density and molecular weight of OHB brushes on the physicochemical properties of prepared copolymers was investigated. PPy substrates were prepared by FeCl₃‐driven oxidative homopolymerization of N‐(2‐carboxyethyl)pyrrole or its copolymerization with pyrrole. The grafting method employed involved controlled anionic polymerization of β‐butyrolactone on pyrrole‐tethered potassium carboxylate active sites. Obtained PPy‐g‐OHB copolymers of varying grafting density and pendant polyester chain length were characterized and the observed structure–property relationships discussed. The impact of real time exposure to phosphate‐buffered saline environment was investigated and the residue products were characterized. Cross‐correlation of spectroscopic, thermal, electrical and elemental analysis data afforded comprehensive evaluation of the structure of prepared materials and their behaviour in hydrolytic medium. Erosion and degradation pathways have been identified, indicating ways to consciously tailor the physicochemical properties of these new biomimetic materials. © 2016 Society of Chemical Industry     

The effect of reaction product on the rate of addition of acetic acid to epichlorohydrin in the presence of chromium(III) acetate

The kinetics of addition of acetic acid to epichlorohydrin carried out in the presence of both the reaction product and chromium(III) acetate catalyst have been studied. At an equimolar ratio of reagents the dilution of the reacting mixture with the reaction product has been found not to affect the reaction order. The presence of product in the starting mixture, as well as temperature increase, considerably reduces the selectivity of reaction. Side reactions of epichlorohydrin are activated. Activation energy, enthalpy and entropy of the reaction all decrease in the presence of reaction product. © 2001 Society of Chemical Industry     

The Impact of Zeta Potential and Physicochemical Properties of TiO2‐Based Nanocomposites on Their Biological Activity

The aim of this research was to observe the relationship between zeta potential, morphology, surface area, porosity, chemical composition, and ecotoxicity of nanocomposite powders such as Au/TiO₂, Ag₂O/TiO₂, PdO/TiO₂, Ag/TiO₂/SiO₂, Ag/N(C)TiO₂, and SiO₂/TiO₂ from which Ag₂O/TiO₂, Ag/N(C)/TiO_2, and Ag/TiO₂/SiO₂ were exhibiting good antimicrobial properties. It was observed, that nanomaterials characterized by similar morphology and zeta potential revealed the similar toxic behavior. The samples of higher agglomeration and higher zeta potential, especially Ag/TiO₂/SiO₂ xerogel and TiO₂/SiO₂ aerogel were generally less ecotoxic to water organisms and plants. They were also not genotoxic in concentrations up to 500 and 250 mg/L, respectively.     

Effects of some technological processes on glucosinolate contents in cruciferous vegetables

Effects of blanching, boiling and freezing of selected cruciferous vegetables (Brussels sprouts, white and green cauliflower, broccoli, and curly cale) on their glucosinolate (GLS) contents were determined. It was found that blanching and cooking of the vegetables led to considerable (P < 0.05) losses of total GLS, from 2.7 to 30.0% and from 35.3 to 72.4%, respectively. No systematic changes in total GLS were found in the vegetables that were blanched and frozen for 48 h. In addition, the highest concentration of cancer-protective compounds, such as aliphatic and indole GLS, were found in Brussels sprouts (sinigrin and glucobrassicin) and in broccoli (glucoraphanin).     

Poly-o-phenylenediamine as redox mediator for laccase

Electrocatalytic activity towards oxygen reduction of fungal laccase entrapped in poly-o-phenylenediamine (POPDA) matrix on glassy carbon electrodes was studied. Cyclic voltammetry and amperometric responses to dissolved oxygen were investigated in pH range from 2 to 6. POPDA reveals a unique ability to serve as a redox mediator for laccase and immobilizing matrix at the same time. The entrapped enzyme efficiently catalyzes reduction of molecular oxygen without any additional mediators. The electrocatalytic current reaches 0.1 mA/cm⁻² per 1 μg of immobilized enzyme on cyclic voltammograms recorded at 1 mV/s in a not stirred electrolyte. Current density values are comparable with those revealed by dissolved laccase (60 μg/ml) mediated by hydroquinone and greatly higher than by the mediator less laccase/glassy carbon system. The potential of oxygen reduction is determined by the polymer redox couple. Consequently, the onset of the oxygen reduction shifts from −0.15 V versus Ag/AgCl in pH 6 to +0.05 V versus Ag/AgCl in pH 2. The laccase-POPDA layers immersed in the deaerated solution show fast amperometric responses to addition of the oxygen containing solution. The observed current values depend linearly on the oxygen concentration. Factors affecting the electrocatalytic activity of the laccase-POPDA system, including the layer thickness and the pH value, are studied. The electrodeposited laccase-POPDA films are characterized by infrared spectra. The results prove that the enzyme secondary structure remains unchanged during the entrapment procedure. POPDA matrix structure consists of the phenazine-type polymer according to infrared spectra.     

Nafion‐115/aromatic poly(etherimide) with isopropylidene groups/imidazole membranes for polymer fuel cells

Proton exchange membrane fuel cells (PEMFCs) with Pt/C gas diffusion electrodes and graphite single‐serpentine monopolar plates were constructed based on an aromatic poly(etherimide) with isopropylidene groups (PI)/imidazole (Im) and a popular Nafion‐115 matrix. The electrochemical properties of PEMFCs were tested at 25 and 60°C. The maximum power density of 171 mW/cm² and the maximum current density of 484 mA/cm² were detected for Nafion‐115/PI membrane. For both constructed PEMFCs the efficiency at 0.6 V was found about 41%. Immersion of Nafion‐115 in PI or PI/Im increased the thermal stability and mechanical properties of membranes. Thermal, mechanical properties and morphology of membranes were characterized by TGA, and AFM techniques including force spectroscopy. Interactions between the components in composite membranes were established by FT‐IR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42436.