Corroles as receptors in liquid membrane electrodes and their potentiometric response towards salicylic acid

Here, we report on the application of corroles as analytically active compounds in liquid membrane electrodes (ISE) that are sensitive towards salicylic acid and salicylate.The potentiometric signals generated by corrole-incorporated ISEs strongly depend on the pH of the aqueous sample solution and the membrane composition, such as the presence of lipophilic sites. Corrole incorporating ISEs are characterised by a low detection limit (4.0 × 10⁻⁵ M) and a wide linear range (4.0 × 10⁻⁵ to 5.3 × 10⁻³ M). Also, they are free from interference versus other organic anions.The mechanism of the generation of the potentiometric signals of corrole incorporating ISEs in the presence of salicylate anion, as well salicylic acid, will be discussed.     

Continuous separation,with microfluidics,of the components of a ternary mixture: from vacuum to purge gas pervaporation

The general objective of this paper is to investigate the separation, with microfluidics, of the components of a ternary mixture, when using vacuum or purge gas pervaporation. The ternary mixture considered is a mixture of methanol (MeOH), water (H₂O) and hydrogen peroxide (H₂O₂). In a previous work (Ziemecka in Lab Chip 15:504–511, 2015), we presented the proof of concept of a microfluidic device, which was able to partially separate MeOH from the other components of such a mixture, by using vacuum pervaporation. Here, our goal is to optimize the operation of this device, by considering vacuum pervaporation, but also purge gas pervaporation. First, we provide a mathematical model of the device. This model is used to discuss the influence of the operating parameters on the device operation. To apply this model to the considered mixture, we determined the MeOH and H₂O permeability coefficients of PDMS membranes prepared from different concentrations of the curing agent. The model is then successfully compared to experimental data. The model and the experiments show that high efficiencies can be reached for both vacuum and purge gas pervaporation, provided a fine-tuning of the operating parameters. For instance, a good efficiency of the vacuum pervaporation is reached at high temperature and low pressure. For purge gas pervaporation, it is reached for low temperature and high pressure.     

A sensitivity analysis of powder forging processes

The purpose of this paper is to analyze the sensitivity problems in metal forming of rigid-visco-poroplastic materials. A repressing powder forging process is analyzed. Parameter sensitivity, material derivative, and control volume approaches to shape sensitivity analysis are presented, analyzed, and compared. Discretization of the continuum expressions is presented. The numerical solutions for parameter sensitivity in forging problems have been described. Numerical examples concerning simple compression test of cylindrical porous specimen are presented.     

Effect of polymer structure on the molecular dynamics and thermal behavior of poly(allyl acetoacetate) and copolymers

In this paper, dielectric and calorimetric studies of the small-molecule glass former allyl acetoacetate monomers as well as its newly synthetized homopolymer and copolymers with different styrene composition were performed in both the liquid and glassy states. The molecular dynamics studies by the broadband dielectric spectroscopy and the stochastic temperature modulated differential scanning calorimetry enabled us to explore relaxation processes of examined materials in the wide frequency range. We found that the copolymers reveal two co-existing glass transitions characterized by the glass transition temperatures, which are very close to those of the corresponding homopolymers. These results suggest that the copolymers exhibited some sequences of acetoacetate units with a microphase-separated morphology in agreement with the value of reactivity ratio previously determined. We investigated effects of copolymerization compositions on the glass transition temperature, the isobaric fragility index, the dielectric and calorimetric intensity, and the dynamic heterogeneity on the glass transitions of the materials.     

The layers of history: New architecture interventions in castle ruins

This paper aims to analyse new architectural works that were created within the ruins of castles and fortifications. The contribution addresses the question whether it is possible to indicate common features in these types of objects, by studying what changed and how it changed in the complexes of historic ruins by introducing a new layer: a new form in their space. The analysis covers eight complexes of castle ruins located in Europe, all being important elements of local historical heritage, all preserved in their historical forms as permanent ruins. Such places are characterised by high imageability, which is conducive to maintaining interest, despite political or ideological changes. The need to introduce new functions, which is connected with this interest, raises questions related to preserving the identity and authenticity of the place, while at the same time building relationships with modern architecture. The research concerned examples from Europe, mostly post-competition works. Research and analysis have shown that all the objects are characterised by well thought-out urban solutions and carefully selected locations of new buildings within the existing historic ruins, thereby helping maintain the structural order between the existing and the new spatial forms. Interventions within the castle ruins were carried out using modern architectural language, using modern techniques and solutions, with great attention to detail. They are characterised by the abstraction of new forms and the creative reinterpretation of existing architectural elements and material solutions of the monuments. The consciously applied contrast of forms and materials means that the historical heritage is being rediscovered, enriched with new, currently necessary functions. In all the described works, the introduction of new spatial experiences within existing objects constituted a significant value. The examples analysed show that the experience and analysis of the broadly understood historical, urban and architectural context are conducive to the creation of valuable architectural works. The characteristics of these examples may contribute to a broader debate on the dialogue between historical heritage and contemporary architecture.     

Changes of chemical composition and dough rheology in two fractions of sieve‐classified Polish spring wheat flour

The study of chemical composition and dough rheology changes in sieve‐classified two fractions (up to 60 and 60–240 μm particles) of wheat flour was the subject of this study. The straight grade flours were obtained by the milling of three Polish varieties of spring wheat, differing in ?? abbreviation? (PSI) values. The flours were separated with the use of a SZ‐1 laboratory sifter. The yield of fine fraction was in the range 50.0–55.7%. The obtained fractions were assayed for the content and composition of free lipids, gluten proteins, damaged starch, ash, water absorption and amylograph viscosity. Dough rheology (extrusion in OTMS cell, alveograph and farinograph tests) and baking trials were also performed. The content of free lipids, including the non‐polar and phospholipids was lower and the content of glycolipids was higher in fine flours. Those fractions were more rich in linoleic acid but the lower content of oleic and linolenic acids resulted in a higher oxidizability index of free lipids. Fine flours contained less ash and significantly more damaged starch. At the same time, they were characterized by a higher content of wet gluten, water absorption, amylograph viscosity and better dough parameters. This was reflected in the bread volume, which was higher by 6.3–10.7%. The influence of the changes in composition and the content of free lipids upon the rheology of the dough after the 90 days flour storage has not been defined unambiguously and requires further research.     

Structure‐Based Mechanism of Oleate Hydratase from Elizabethkingia meningoseptica

Hydratases provide access to secondary and tertiary alcohols by regio‐ and/or stereospecifically adding water to carbon‐carbon double bonds. Thereby, hydroxy groups are introduced without the need for costly cofactor recycling, and that makes this approach highly interesting on an industrial scale. Here we present the first crystal structure of a recombinant oleate hydratase originating from Elizabethkingia meningoseptica in the presence of flavin adenine dinucleotide (FAD). A structure‐based mutagenesis study targeting active site residues identified E122 and Y241 as crucial for the activation of a water molecule and for protonation of the double bond, respectively. Moreover, we also observed that two‐electron reduction of FAD results in a sevenfold increase in the substrate hydration rate. We propose the first reaction mechanism for this enzyme class that explains the requirement for the flavin cofactor and the involvement of conserved amino acid residues in this regio‐ and stereoselective hydration.     

The Effect of Antibacterial Particle Incorporation on the Mechanical Properties,Biodegradability, and Biocompatibility of PLA and PHBV Composites

The composites based on polylactide (PLA) and poly (3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) with the addition of antibacterial particles: silver (Ag) and copper oxide (CuO) are characterized. Basic mechanical properties and biodegradation processes, as well as biocompatibility of materials with human cells are determined. The addition of Ag or CuO to the polymers do not significantly affect their mechanical properties, flammability, or biodegradation rate. However, several differences between the base materials are observed. PLA‐based composites have higher tensile and impact strength values, while PHBV‐based ones have a higher modulus of elasticity, as well as better mechanical properties at elevated temperatures. Concerning biocompatibility, each of the tested materials support the growth of fibroblasts over time, although large differences are observed in the initial cell attachment. The analysis of hydrolytic degradation effects on the structure of materials shows that PHBV degrades much faster than PLA. The results of this study confirm the good potential of the investigated biodegradable polymer composites with antibacterial particles for future biomedical applications.