Conformation of Chains in Cores of Block Copolymer Micelles with Solubilized Homopolymer: a Monte Carlo Study

A system of compatible self‐avoiding polymer chains solubilized in spherical cores of block copolymer micelles was studied by lattice Monte Carlo simulations. The core is modeled as a spherical cavity on a simple cubic lattice, filled in partially by tethered (core‐forming) chains and partially by free (solubilized) chains. Molecular parameters (e.g., the ratio of the contour length of the model chains to the core radius) correspond to those in real micellar systems. The density (the fraction of lattice sites occupied) is 0.6 which corresponds to swollen micellar cores in real micellar systems. Simulations yield a constant segment density profile in the core. Both the tethered and solubilized chains acquire an ellipsoidal shape. The ellipsoids equivalent to both types of chains are more spherical than those in a melt and strongly oriented. The chains in the core show a Gaussian‐like behavior. Minor deviations from Gaussian behavior for tethered chains are due to surface effects.     

Antimicrobial and Anticancer Application of Silver(I) Dipeptide Complexes

Three silver(I) dipeptide complexes [Ag(GlyGly)]_n(NO₃)_n (AgGlyGly), [Ag₂(GlyAla)(NO₃)₂]_n (AgGlyAla) and [Ag₂(HGlyAsp)(NO₃)]_n (AgGlyAsp) were prepared, investigated and characterized by vibrational spectroscopy (mid-IR), elemental and thermogravimetric analysis and mass spectrometry. For AgGlyGly, X-ray crystallography was also performed. Their stability in biological testing media was verified by time-dependent NMR measurements. Their in vitro antimicrobial activity was evaluated against selected pathogenic microorganisms. Moreover, the influence of silver(I) dipeptide complexes on microbial film formation was described. Further, the cytotoxicity of the complexes against selected cancer cells (BLM, MDA-MB-231, HeLa, HCT116, MCF-7 and Jurkat) and fibroblasts (BJ-5ta) using a colorimetric MTS assay was tested, and the selectivity index (SI) was identified. The mechanism of action of Ag(I) dipeptide complexes was elucidated and discussed by the study in terms of their binding affinity toward the CT DNA, the ability to cleave the DNA and the ability to influence numbers of cells within each cell cycle phase. The new silver(I) dipeptide complexes are able to bind into DNA by noncovalent interaction, and the topoisomerase I inhibition study showed that the studied complexes inhibit its activity at a concentration of 15 μM.     

Monte Carlo study of chain conformations in the swollen middle layer of onion‐skin polymeric micelles

Conformations of chains in swollen middle layers of onion‐skin micelles were studied by Monte Carlo simulations on a tetrahedral lattice under conditions that mimic real systems of swollen onion‐skin micelles. Polymer blocks are modeled as tethered self‐avoiding chains, enclosed in a narrow spherical layer. Average density of segments, 〈g_S〉 ca. 0.6, corresponds to swollen micellar systems. Only the excluded volume effect was taken into account since it plays the most important role in dense polymer systems. Individual chains are described by equivalent ellipsoids of gyration. Distributions of the ellipsoid half‐axes were calculated during simulations. Results based on a large series of simulations indicate that the middle layer‐forming blocks may be described as prolonged ellipsoids oriented preferentially perpendicular to the radial direction. Analysis of the data concerning the orientations of end‐to‐end vectors and distributions of segments within one chain indicates that individual chains are strongly interpenetrated and the multi‐chain system is fairly disordered.     

Lab-scale testing of a low-loaded activated sludge process with membrane filtration

Two membrane bioreactors (MBRs; volume = 300 L) equipped with different types of immersed membrane modules were operated simultaneously under the same laboratory conditions as a low-loaded activated sludge process without any membrane regeneration and excess sludge uptake (sludge retention time SRT up to 170 d; activated sludge concentration MLSS up to 11 g L⁻¹). The aim was to verify the quality of treated water and to study the properties of "very old" activated sludge. Another aim was to compare different selected membrane types and choose the best one for further pilot-scale testing. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

A three-phase nonequilibrium model for catalytic distillation

Nonequilibrium model for steady state simulation of catalytic distillation is presented. Mathematical model takes into account both mass and heat transfers across the gas liquid interface and through the liquid-solid (catalyst) interface. Equations describing the mentioned phenomena are based on the effective diffusivity approach. The resulting system of nonlinear algebraic equations was implemented in the FORTRAN programming language and solved by the BUNLSI (Ferraris & Tronconi, 1986) solver. The described model was verified using the experimental data obtained from a continuous distillation column equipped with catalytic packing. As an experimental model system, synthesis of propyl propionate from propan-1-ol and propionic acid was chosen. Comparison of experimental and simulation data is presented, and appropriateness of the developed model for other types of catalytic distillation processes is discussed. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

Coal as a New Carbon Paste Electrode Modifier with Sorption Properties

A new type of carbon paste electrode modified with subbituminous and bituminous coal is presented. The operability of the coal carbon paste electrode with respect to the working potential window attainable was tested in various electrolytes. Cyclic voltammetry of the reference redox system [Fe(CN)₆]^3?/4? was performed to evaluate electron transfer kinetics. Open‐circuit sorption of Cd(II), Pb(II), and Cu(II) with subsequent anodic stripping voltammetry was used to pilot coal sorption ability. The coal modified carbon paste electrode was also examined as a support for mercury film deposition and anodic stripping voltammetry of metals.     

Functionalized magnetic micro- and nanoparticles: optimization and application to micro-chip tryptic digestion

The preparation of an easily replaceable protease microreactor for micro-chip application is described. Magnetic particles coated with poly(N-isopropylacrylamide), polystyrene, poly(2-hydroxyethyl methacrylate-co-ethylene dimethacrylate), poly(glycidyl methacrylate), [(2-amino-ethyl)hydroxymethylen]biphosphonic acid, or alginic acid with immobilized trypsin were utilized for heterogeneous digestion. The properties were optimized, with the constraint of allowing immobilization in a microchannel by a magnetic field gradient. To obtain the highest digestion efficiency, sub-micrometer spheres were organized by an inhomogeneous external magnetic field perpendicularly to the direction of the channel. Kinetic parameters of the enzyme reactor immobilized in micro-chip capillary (micro-chip immobilized magnetic enzyme reactor (IMER)) were determined. The capability of the proteolytic reactor was demonstrated by five model (glyco)proteins ranging in molecular mass from 4.3 to 150 kDa. Digestion efficiency of proteins in various conformations was investigated using SDS-PAGE, HPCE, RP-HPLC, and MS. The compatibility of the micro-chip IMER system with total and limited proteolysis of high-molecular-weight (glyco)proteins was confirmed. It opens the route to automated, high-throughput proteomic micro-chip devices.     

Synthesis of bis‐intercalators with an aminochloropyrimidine ring as potential anticancer agents

The synthesis of a series of polymethylene chain‐bridged aminochloropyrimidines as potential DNA intercalators is described. N,N'‐Bis(2‐amino‐6‐chloro‐4‐pyrimidyl)‐1,3‐diaminopropane ( 3 ), N,N'‐bis(2‐amino‐6‐chloro‐4‐pyrimidyl)‐1,4‐diaminobutane ( 4 ), N,N'‐bis(2‐amino‐6‐chloro‐4‐pyrimidyl)‐1,6‐diaminohexane ( 5 ), N,N'‐bis(2‐amino‐6‐chloro‐4‐pyrimidyl)‐1,8‐diaminooctane ( 6 ), N,N'‐bis(2‐amino‐6‐chloro‐4‐pyrimidyl)‐1,10‐diaminodecane ( 7 ), and N,N'‐bis(2‐amino‐6‐chloro‐4‐pyrimidyl)‐1,12‐diaminododecane ( 8 ) were synthesized from 2‐amino‐4,6‐dichloropyrimidine ( 1 ) and 1,3‐diaminopropane, 1,4‐diaminobutane, 1,6‐diaminohexane, 1,8‐diaminooctane, 1,10‐diaminodecane, and 1,12‐diaminododecane, respectively. The spectral data and other physical properties of the new compounds are discussed.     

Computer Study of Stimuli-Responsive Polyelectrolyte Micelles in Aqueous Media. Comparison of Monte Carlo and Self-Consistent Field Approaches

The behavior of polyelectrolyte micelles with kinetically frozen hydrophobic cores in aqueous solutions was studied by Monte Carlo (MC) simulations and self-consistent field (SCF) calculations. Some results have already been published. The structure of water-soluble shells formed by weak polyelectrolytes, both pure and containing a low fraction of strongly hydrophobic units arranged either in a short sequence or distributed uniformly in the shell-forming chains was studied in detail. In the case of sequenced system, the analysis of concentration profiles of individual species reveals strong segregation and important self-organization of hydrophobic units in the shell. A comparison and critical analysis of results of MC and SCF methods is presented.     

Determination of Selected Chlorinated Priority Substances in Fish using QuEChERS Method with Dual dSPE Clean-up and Gas Chromatography

A rapid and simple analytical method for the determination of ten chlorinated priority substances (hexachloro-1,3-butadiene, pentachlorobenzene, hexachlorobenzene, hexachlorocyclohexane isomers, heptachlor, and heptachlor epoxides) in fish samples using QuEChERS extraction, dual dispersive solid-phase extraction (dSPE) clean-up, and GC analysis was developed. For the extraction, two published extraction/partitioning procedures were evaluated, and the recoveries obtained for the analytes (in range 54–98 % with RSDs ≤15 %) were in favour of the conventional QuEChERS method. The use of the dual dSPE clean-up yields cleaner extracts than in the case of single dSPE, which enables the use of ECD for the detection of the analytes and simplifies the maintenance of the GC system. The method was optimised using homogenates of chub fish that is frequently sampled for monitoring purposes. The linearity of the method was evaluated using matrix-matched calibration curves (in the range 2–50 μg kg⁻¹), and correlation coefficients (r ²) in the range 0.9927–0.9992 and RSDs of the relative response factors (RRF) below the value of 20 % were achieved. LODs ranged from 0.5 to 1.1 μg kg⁻¹, while LOQs ranged from 1.5 to 3.5 μg kg⁻¹. The accuracy of the method was verified by the analysis of the NIST standard reference material SRM 1946 (Lake Superior Fish Tissue), and most of the analytes of interest presented good agreement with the certified values.