Amphiphilic behaviour of poly(glycidol)-based macromonomers and its influence on homo-polymerisation in water and in water/benzene mixture

The properties of amphiphilic polyether macromonomers and their behaviour during homo-polymerisation in water and in water/benzene mixture are reported. Homo-poly(glycidol) macromonomer bearing polymerisable p-vinyl benzyl end groups (PGl55-St) and two block poly(glycidol)-b-poly(glycidyl phenyl ether) macromonomers, containing polymerisable p-vinyl benzyl end groups attached to the hydrophobic (PGl52-b-PGlPhE8-St) or hydrophilic (PGlPhE9-b-PGl54-St) block were used for investigations. DLS measurements showed formation of micelles by all macromonomers, what is the reason for enhanced homo-polymerisation. In water the polymerisation initiated with 4,4′-azobis(4-cyanovaleric acid) was fast, while macromonomer conversion was over 90%. Introduction of benzene to the polymerisation system resulted in formation of swollen (less packed) micelles and to a decrease of the local concentration of double bonds in the micelle core. As a result the decrease of reaction rate followed by longer polymerisation time in case of PGl55-St and PGl52-b-PGlPhE8-St was observed. Nevertheless, their conversion remained high and varied from 95 to 10. In contrast for PGlPhE9-b-PGl54-St increase of polymerisation rate, accompanied by slight increase of conversion was observed for homo-polymerisation in water/benzene mixture.     

Safety aspects in modelling and operating of batch and semibatch stirred tank chemical reactors

Safety aspects in modelling of batch and semibatch stirred tank reactors as well as a model based safety analysis have been considered. Applicability of two basic types of models – i.e. the perfectly mixed reactor model and the CFD model, both formulated for laboratory scale as well as pilot plant scale reactors – has been discussed. A formulation of the appropriate reactor model, which is adequate to the considered case study has been demonstrated and tested experimentally. Particular attention has been devoted to the formulation of robust CFD models employed to simulate a performance of the stirred tank reactors. It has been found that models for perfectly mixed reactors may have quite wide range of application, while the CFD models should be definitely used in case of fast reactions, high viscosity of the reacting mixture as well as of failure leading to stopping of the impeller. The CFD models are able to predict a dynamic behaviour of reactors at any circumstances, so they can play a significant role in safety analysis carried out for industrial scale reactors, for which experimental safety tests are expensive and dangerous.     

A microporous and high surface area active carbon obtained by the heat-treatment of chitosan

A method is described for converting chitosan into a high surface area and porous active carbon using a Na₂CO₃ solution impregnated into a partly depolymerized, protonated and water soaked chitosan. The wet chitosan paste is heat treated and transformed into a nonporous solid i.e. a carbon-rich matrix with uniformly suspended Na₂CO₃ nanocrystallites. Subsequent HCl etching opens cavities in the matrix due to the removal of the Na₂CO₃. The active carbon is high surface area (above 400 m²/g), microporous (below 1 nm) and nitrogen-rich (above 6% atomic).     

Surface modification of macroporous poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) resins for improved Candida antarctica lipase B immobilization

Crosslinked macroporous hydrophilic poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [abbreviated poly(GMA-co-EGDMA)] with identical chemical structure (60% of glycidyl methacrylate) but with varied average pore sizes (from 30 to 560 nm), specific surface areas (from 13.2 to 106.0 m²/g), specific volumes (from 0.755 to 1.191 cm³/g) and particle sizes (<100 μm–630 μm) were synthesized via suspension polymerization. Modifications of poly(GMA-co-EGDMA) with various diamines (1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane and 1,8-diaminooctane), 2-fluoroethylamine, glutaraldehyde and cyanuric chloride were carried out. The influence of the interaction between Candida antarctica lipase B (Cal-B) and various carriers during immobilization on the loading and hydrolytic activity (hydrolysis of para-nitrophenyl acetate) of the immobilized Cal-B were studied. Immobilization of Cal-B was performed at different temperatures and pH values. Cal-B immobilized at 30 °C and pH 6.8 was leading to increased activities. Purely physical adsorption between enzyme and copolymer was observed on carriers in which amine or fluorine groups were introduced into the carrier structure by modification with various diamines or 2-fluoroethylamine. As a consequence enzyme loading and activity decreases. In contrary, modification of the poly(GMA-co-EGDMA) with glutaraldehyde and cyanuric chloride results in a covalent connection between enzyme and carrier. The obtained results show a significant increase in Cal-B activity. The influence of the amount of glutaraldehyde and cyanuric chloride used for modification was screened. Increasing the amount of glutaraldehyde or cyanuric chloride used for modification resulted in an increase of the enzyme loading. Consequently, higher amount of glutaraldehyde used led to a higher fraction of the enzyme molecules that are covalently connected on to the carrier. As the amount of glutaraldehyde or cyanuric chloride used for modifications increases, activity of immobilized C. antarctica lipase B primarily increases, showing the highest value for 0.66% and 0.050% w/w, respectively, and subsequently decreases. We could show that Cal-B immobilized on epoxy-containing copolymer modified with glutaraldehyde and cyanuric chloride performs higher activity than free enzyme powder.     

Enabling resilient P2P video streaming: survey and analysis

Peer-to-Peer (P2P) techniques for multimedia streaming have been shown to be a good enhancement to the traditional client/server methods when trying to reduce costs and increase robustness. Due to the fact that P2P systems are highly dynamic, the main challenge that has to be addressed remains supporting the general resilience of the system. Various challenges arise when building a resilient P2P streaming system, such as network failures and system dynamics. In this paper, we first classify the different challenges that face P2P streaming and then present and analyze the possible countermeasures. We classify resilience mechanisms as either core mechanisms, which are part of the system, or as cross-layer mechanisms that use information from different communication layers, which might inflict additional costs. We analyze and present resilience mechanisms from an engineering point of view, such that a system engineer can use our analysis as a guide to build a resilient P2P streaming system with different mechanisms and for various application scenarios.     

Influence of Soft Cocoa Butter Equivalents on Color and Other Physical Attributes of Chocolate

The physical characteristics and color of chocolate depend on the physical properties and crystallization behavior of the fat phase. In this study, the fat phase of chocolate samples contains cocoa butter from Ghana and soft cocoa butter equivalent (CBE). The laboratory-made chocolate samples were tempered at three different precrystallization temperatures (25, 27 and 29 °C), using three different concentrations of CBE (3, 5 and 7%), calculated as percentage of the chocolate. Physical characteristics of chocolate, namely thermoreographic parameters and solid fat content (SFC), were measured. The color of the chocolate was determined instrumentally, before and after thermo-cycle testing at 32/20 °C. It was found that CBE changed the melting properties of chocolate produced with cocoa butter from Ghana, which is of moderate hardness. It was determined that the optimum precrystallization temperature for chocolate mass with addition of CBE in the given conditions of measurement was 27 °C, the temperature that resulted in the best fat bloom resistance.     

Analysis of the strain and hardness in self-cured and light-cured self-adhesive resin based cement

The study showed an application of the 3?D Digital Image Correlation Method (3?D-DIC) for detection of von Mises strain in samples of the self-etch, self-adhesive resin based cement (RBC). The aim was to determine and compare strain in the self-cured and light-cured Maxcem Elite, furthermore to investigate the hardness of these two cement-types. The experiment was carried out using two groups of Maxcem Elite (Kerr, Orange, CA, USA) samples; each tested group includes five (ø5?×?2?mm sized) samples, for both self-curing and light-curing mode. All samples were prepared by filling teflon ring-type molds. In addition, Vickers micro-hardness was measured for all samples. Maxcem Elite showed similar maximum strain values from 10% to 12% for both groups. Besides the maximum strain value, the 3?D-DIC method also enabled monitoring the change of strain field even after the recommended polymerization time. This method has shown that the polymerization shrinkage continues even after 10?min which disagreed with manufacturer’s suggestion. Group II showed maximum strain values of 12% in the peripheral zone after 10?min, in the last Stage (Stage 60). Statistically significant difference was not found in the overall strain between self- and light-cured Maxcem Elite neither peripherally (p?=?0.118) nor centrally (p?=?0.879). However, statistical significance was found in strain regarding central and peripheral zone in both, self-cured (p?=?0.020) and light-cured (p?=?0.002) Maxcem Elite. The mean von Mises strain values in the periphery of the samples (Section 0) were significantly higher compared to strain values in the center of the samples (for Section 1 and 2). The last stage (Stage 60) of the light-cured Maxcem Elite polymerization showed significantly higher values of von Mises strain compared to initial stage (Stage 0). Higher values of micro-hardness were noticed on the surfaces directly exposed to LED lamp after performing measurements of micro-hardness on light-cured samples.     

The role of MCM-41 composition in the creation of basicity by alkali metal impregnation

Three types of mesoporous molecular sieves (silicate MCM-41, niobosilicate NbMCM-41, and aluminosilicate AlMCM-41) were impregnated with alkali metal acetates. The textural stability of the samples was estimated on the basis of XRD measurements and nitrogen adsorption/desorption methods. The acidic–basic properties of the obtained materials were tested in the cyclization of acetonylacetone and studied by FTIR spectroscopy after adsorption of methylacetylene (propyne) and pyridine. Two types of chemical reactions between mesoporous matrix and alkali metal salt/oxide were observed: the reaction between alkali metal salt and silica/silicate and the reaction between basic oxide and silanol groups or Na⁺ cations. In the first one the alkali metal silicate formation decreases from Li to Cs species and leads to the destruction of the material. The second reaction places alkali metal cations in extra framework positions, which increases from Li to Cs species and is only observed in the case of AlMCM-41 and NbMCM-41 materials. As a result of the second reaction Lewis acidity is generated. The average effect of these two interactions leads to the volcanic curve for basicity of M/AlMCM-41 and M/NbMCM-41 with the maximum for K-samples. In contrast, basicity of M/MCM-41 systematically increases from Li to Cs form since the second type of interaction does not occur for these samples.