Deoxycytidine kinase (dCK) uses either ATP or UTP as phosphoryl donors to catalyze the phosphorylation of nucleoside acceptors. The kinetic properties of human dCK are modulated in vivo by phosphorylation of serine 74. This residue is a part of the insert region and is situated distant to the active site. Replacing the serine with a glutamic acid (S74E variant) can mimic phosphorylation of Ser74. To understand how phosphorylation affects the catalytic properties of dCK, we examined the S74E variant of dCK both structurally and kinetically. We observe that the presence of a glutamic acid at position 74 favors the enzyme adopting the open conformation. Glu74 stabilizes the open conformation by directly interacting with the indole side chain of Trp58, a residue that is in close proximity to the base of the nucleoside substrate. The open dCK conformation is competent for the binding of nucleoside but not for phosphoryl transfer. In contrast, the closed conformation is competent for phosphoryl transfer but not for product release. Thus, dCK must transition between the open and closed states during the catalytic cycle. We propose a reaction scheme for dCK that incorporates the transition between the open and closed states, and this serves to rationalize the observed kinetic differences between wild type dCK and the S74E variant.
Industrial waste from the production of metallic silicon and silicon–iron alloys, which includes silica fumes (microsilica), is subject to numerous applications aiming at its reuse in concrete and polymeric composites. Recycling solves the problem of their storage and adverse environmental impact. Six different formulas of epoxy resins were tested, differing in the type of polymer, the mixing process (sonication or not) and the presence of microsilica. The study showed that microsilica added to the epoxy resin changes its viscosity and free surface energy, and these are the parameters that determine the adhesion of the polymer to the concrete surface. Strength tests and SEM analysis have determined how microsilica molecules can penetrate the structure of polymer macromolecules by filling and forming temporary chemical bonds. Mixing the fillers with the adhesive was achieved by using a sonication process. The analysis of the obtained results showed that, depending on the initial composition of the polymer, the addition of microsilica can change the chemical, physical and mechanical properties of the hardened adhesive to varying degrees. In the case of adhesives used in the construction industry to strengthen and glue structural elements, these changes significantly affect the durability of the adhesive joints.
Abstract:The article presents a proposal of a model of fatigue destruction of hydrophobised ceramic brick, i.e., a basic masonry material. The brick surface was hydrophobised with two inorganic polymers: a nanopolymer preparation based on dialkyl siloxanes (series 1-5) and an aqueous silicon solution (series 6-10). Nanosilica was added to the polymers to enhance the stability of the film formed on the brick surface. To achieve an appropriate blend of the polymer liquid phase and the nano silica solid phase, the mixture was disintegrated by sonication. The effect of the addition of nano silica and sonication on changes in the rheological parameters, i.e., viscosity and surface tension, was determined. Material fatigue was induced by cyclic immersion of the samples in water and drying at a temperature of 100 • C, which caused rapid and relatively dynamic movement of water. The moisture and temperature effect was determined by measurement of changes in surface hardness performed with the Vickers method and assessment of sample absorbability. The results provided an approximate picture of fatigue destruction of brick and hydrophobic coatings in relation to changes in their temporal stability. Additionally, SEM images of hydrophobic coatings in are shown.
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