[Cu(X-salicylato)2(N,N-diethylnicotinamide)2(H2O)2] complexes: conformational polymorphism and its consequence in supramolecular hydrogen-bonding networks formation

Novel copper(II) X-salicylate complexes with N,N-diethylnicotinamide (dena) of the formula [Cu(RCOO)₂(dena)₂(H₂O)₂] (RCOO = 3-methylsalicylate anion (3-Mesal, 1), 4-methylsalicylate anion (4-Mesal, 2), 5-methylsalicylate anion (5-Mesal, 3), 5-methoxysalicylate anion (5-MeOsal, 4) or 4-methoxysalicylate anion (4-MeOsal, 5)), and complex [Cu(3-MeOsal)₂(dena)₂(H₂O)₂]∙2H₂O (3-MeOsal = 3-methoxysalicylate anion (6)) have been prepared in the crystalline forms and characterized by spectroscopic methods (IR, Vis–UV, EPR). All the compounds according to their composition (1–5) seem to possess octahedral copper(II) stereochemistry. The complex 1 has been prepared in two different forms. X-ray analyses of the complexes 1, 4, and 5 were carried out and they featured a tetragonal-bipyramidal geometry around the copper atoms. The tetragonal planes are created by X-salicylate anions bonded to the copper(II) atoms via unidentate carboxylate oxygen atoms and the pyridine ring nitrogen atoms of the neutral ligand N,N-diethylnicotinamide, while in axial positions are water molecules. The two forms of complex 1 present conformation polymorphs and supramolecular isomers.     

Synthesis and antimicrobial activity of a series of optically active quaternary ammonium salts derived from phenylalanine

We synthesized nine quaternary ammonium compounds (QUATs) starting from phenylalanine, N-alkyl-N,N-dimethyl-(1-hydroxy-3-phenylpropyl)-2-ammonium bromides, which were prepared as optically pure substances. Five compounds were prepared as S-enantiomers and four compounds as R-enantiomers. These compounds were evaluated by their activities against bacteria and fungi. Three microbial strains were used in the study: the gram-negative bacteria Escherichia coli, the gram-positive bacteria Staphylococcus aureus and the fungi Candida albicans. The activities were expressed as minimum bactericidal or fungicidal concentrations (MBC). The most active compounds were (2S)-N-tetradecyl-N,N-dimethyl-(1-hydroxy-3-phenylpropyl)-2-ammonium bromide and (2R)-N-tetradecyl-N,N-dimethyl-(1-hydroxy-3-phenylpropyl)-2-ammonium bromide, with MBC values exceeding those of commercial benzalkoniumbromide (BAB) used as standard. The relationships between structure and biological activity of the tested QUATs were quantified by the bilinear model (QSAR) and are discussed.     

Specific molecular and cellular events induced by irradiated X‐ray photoactivatable drugs raise the problem of co‐toxicities: particular consequences for anti‐cancer synchrotron therapy

Synchrotrons are capable of producing intense low‐energy X‐rays that enable the photoactivation of high‐Z elements. Photoactivation therapy (PAT) consists of loading tumors with photoactivatable drugs and thereafter irradiating them at an energy, generally close to the K‐edge of the element, that enhances the photoelectric effect. To date, three major photoactivatable elements are used in PAT: platinum (cisplatin and carboplatin), iodine (iodinated contrast agents and iododeoxyuridine) and gadolinium (motexafin gadolinium). However, the molecular and cellular events specific to PAT and the radiobiological properties of these photoactivatable drugs are still misknown. Here, it is examined how standard and synchrotron X‐rays combined with photoactivatable drugs impact on the cellular response of human endothelial cells. These findings suggest that the radiolysis products of the photoactivatable drugs may participate in the synergetic effects of PAT by increasing the severity of radiation‐induced DNA double‐strand breaks. Interestingly, subpopulation of highly damaged cells was found to be a cellular pattern specific to PAT. The data show that the efficiency of emerging anti‐cancer modalities involving synchrotron photoactivation strongly depends on the choice of photoactivatable drugs, and important series of experiments are required to secure their clinical transfer before applying to humans.     

Polysulfobetaine films prepared by electrografting technique for reduction of biofouling on electroconductive surfaces

The sulfobetaine films were prepared on stainless steel and golden surfaces. In the first step, the poly(2-(dimethylamino)ethyl methacrylate) film was created by employing the electrografting polymerization technique. In the second step, this film was modified to polysulfobetaine, i.e. the polymer film bearing the zwitterionic groups. The presence of the electrografted film and its modification were determined by contact angle measurements, infrared spectroscopy in reflectance mode and X-ray photoelectron spectroscopy. The prepared films were homogeneous with the thickness from about 5 to 26 nm as determined by X-ray photoelectron spectroscopy. The atomic force microscopy measurements showed the increase of surface roughness upon the surface coating. In vitro tests using adherent RAT-2 fibroblast cells and fluorescently labelled bovine serum albumin proteins showed that prepared polysulfobetaine films can be used in applications requiring the resistance against cell attachment and biofouling.     

On super-linear Emden–Fowler type differential equations

We study the second order Emden–Fowler type differential equation

(a(t)|x^′|^αsgnx^′)^′+b(t)|x|^βsgnx=0${(a(t){\left|x^{\prime }\right|}^{\alpha }\mathrm{sgn}{x}^{\prime })}^{\prime }+b(t){|x|}^{\beta }\mathrm{sgn}x=0$

in the super-linear case α<β$\alpha <\beta$. Using a Hölder-type inequality, we resolve the open problem on the possible coexistence on three possible types of nononscillatory solutions (subdominant, intermediate, and dominant solutions). Jointly with this, sufficient conditions for the existence of globally positive intermediate solutions are established. Some of our results are new also for the Emden–Fowler equation.     

Theoretical study on transesterification in a combined process consisting of a reactive distillation column and a pervaporation unit

Steady state analysis of a combined hybrid process consisting of a reactive distillation column, pervaporation unit, and a distillation column is presented. This process configuration was first presented by Steinigeweg and Gmehling (2004) for the transesterification of methyl acetate and butanol to butyl acetate and methanol. This system is characteristic for its low reaction rate and complex phase equilibrium. Steinigeweg and Gmehling (2004) have shown that the combination of reactive distillation and pervaporation is favourable since conversions close to 100 % can be reached with a reasonable size of the reactive section in the reactive distillation column. The aim of this paper is to show that although high conversion can be achieved, very complicated steady state behaviour must be expected. The presented analysis is based on mathematical modelling of a process unit, where the steady-state analysis, including continuation and bifurcation analyses, was used. Multiple steady states were predicted for the studied system; three steady states with conversions higher than 98 %. However, not all predicted steady states met the maximal allowed temperature condition in the reactive section (catalyst maximal operation temperature of 393 K). The presence of multiple steady states reduces the operability and controllability of the reactive distillation column during its start-up and during the occurrence of any variation of operating parameters because the system can be shifted from one steady state to another one (concurrent exceeding the maximal allowed temperature) with unwanted consequences, e.g. production loss. Therefore, design and subsequent operation of such a complicated system is an ambitious task requiring knowledge of any possible system behaviour.     

Hydrogen‐Bond‐Based Magnetic Exchange Between μ‐Diethylnicotinamide(aqua)bis(X‐salicylato)copper(II) Polymeric Chains

Polymeric salicylatocopper(II) complexes of unusual composition [C u(X‐ sal)₂( μ‐denia)(H₂O)]_n [denia = diethylnicotinamide, and X‐sal = 5‐methylsalicylate ( 1 ), 3‐methylsalicylate ( 2 ), 4‐methoxysalicylate ( 3 ), 3,5‐dichlorosalicylate ( 4 ) and 3,5‐dibromosalicylate ( 5 )] were synthesized and characterized. Magnetic measurements were performed in the temperature range 1.8–300 K. The structural unit of all complexes consists of a Cu^II atom, which is monodentately coordinated by the pair of X‐salicylate anions in trans positions. Water and the diethylnicotinamide ligand occupy the other two basal plane positions of the tetragonal pyramid. The axial positions are occupied by a diethylnicotinamide oxygen atom of neighboring structural units, thus forming a spiral polymeric structure parallel to b axis. Magnetic measurements showed that all complexes 1 – 5 exhibit a susceptibility maximum at about 6–8 K. The obtained data fit to Bleaney–Bowers equation gave singlet‐triplet energy gaps 2J = –8.60 cm^–1 for 1 , 2J = –6.57 cm^–1 for 2 , 2J = –8.57 cm^–1 for 3 , 2J = –6.82 cm^–1 for 4 , and 2J = –6.45 cm^–1 for 5 . The supramolecular structure based on hydrogen bonds [described by supramolecular synthons R₂²(10) and R₂²(12)] is the pathway for antiferromagnetic interactions of the magnetically coupled pairs of copper atoms of neighboring chains within the 2D supramolecular layers. The results of the magnetic measurements suggest involvement of the COO groups in the magnetic interaction pathway for all five complexes.     

Photoinduced superoxide radical anion and singlet oxygen generation in the presence of novel selenadiazoloquinolones (an EPR Study)

Novel 7‐substituted 6‐oxo‐6,9‐dihydro[1,2,5]selenadiazolo[3,4‐h]quinoline ( SeQ(1–6) ) and 8‐substituted 9‐oxo‐6,9‐dihydro[1,2,5]selenadiazolo[3,4‐f ]quinoline derivatives ( SeQN(1–5) ) with R₇, R₈ = H, COOC₂H₅, COOCH₃, COOH, COCH₃ or CN were synthesized and their spectral characteristics were obtained by UV/Vis spectroscopy. Ultraviolet A photoexcitation of the selenadiazoloquinolones in dimethylsulfoxide or acetonitrile resulted in the formation of paramagnetic species coupled with molecular oxygen activation generating the superoxide radical anion or singlet oxygen, evidenced by electron paramagnetic resonance spectroscopy. The cytotoxic/photocytotoxic impact of selenadiazoloquinolones on murine and human cancer cell lines was demonstrated using the derivative SeQ5 (with R₇ = COCH₃).     

Indirect voltammetric detection of fluoride ions in toothpaste on a comb-shaped interdigitated microelectrode array

A novel technique based on dynamic electrochemistry for the detection of fluoride ions was developed. It is based on its strong complexation with ferric ion. Formed fluoroferric complex is cathodically inactive at the potential of the reduction of free ferric aquo ion. The voltammetric and amperometric response of platinum comb-shaped interdigitated microelectrode array is decreased after fluoride addition. This decrease serves for the quantification of fluoride ions added to the solution. The detection limit of 4.5 × 10⁻⁵ mol dm⁻³ was achieved when one of the segments of interdigitated microelectrode array (IDA) was used as an indicating electrode. The detection limit is about one order of magnitude lower than in the case of conventional platinum macroelectrode. In comparison with ISE electrodes this method is faster and also avoiding large error resulting from the antilogarithmization of ISE Nerstian response. The method was applied to the analysis of toothpaste.     

Stabilization effect of potential antioxidants on the thermooxidative stability of styrene–butadiene rubber

Effects of several heterocyclic compounds containing nitrogen, trisubstituted amines and diamines and molecules based on N,N,N′,N′,N′′,N′′-substituted-[1,3,5]triazine-2,4,6-triamine in preventing thermooxidative degradation of styrene–butadiene rubber (SBR) have been studied using non-isothermal DSC measurements. The aim of this study was to determine and compare the stabilizing effect of individual compounds and to select the structures with the best antioxidative properties. In order to compare the stabilizing effect of the compounds, induction periods and protection factors have been calculated. The treatment of the experimental data was carried out using a method based on a non-Arrhenian temperature function. The results show that better antioxidative properties can be assigned to heterocyclic compounds. On the other hand, molecules containing triazine structures exhibited only negligible stabilizing effect on SBR at lower temperatures and even destabilizing effect at higher temperatures.