Selective Binding of Cyclodextrins with Leflunomide and Its Pharmacologically Active Metabolite Teriflunomide

The selectivity of encapsulation of leflunomide and teriflunomide by native α-, β- and γ-cyclodextrins was investigated through ¹H NMR and molecular modeling. Thermodynamic analysis revealed the main driving forces involved in the binding. For α-cyclodextrin, the partial encapsulation was obtained while deep penetration was characterized for the other two cyclodextrins, where the remaining polar fragment of the molecule is located outside the macrocyclic cavity. The interactions via hydrogen bonding are responsible for high negative enthalpy and entropy changes accompanying the complexation of cyclodextrins with teriflunomide. These results were in agreement with the molecular modeling calculations, which provide a clearer picture of the involved interactions at the atomic level.     

Prediction of ring crack initiation in ceramics and glasses using a stress–energy fracture criterion

Crack initiation in brittle materials upon spherical indentation is associated with the tensile radial stresses during loading. However, location of crack onset often differs (offset) from the site of maximal stress. In addition, experiments reveal a strong dependency of crack initiation forces on geometrical parameters as well as the surface condition of the sample. In this work, a coupled stress–energy fracture criterion is introduced to describe the initiation of ring cracks in brittle materials, which takes into account the geometry of the contact and the inherent strength and fracture toughness of the material. Several experiments reported in literature are evaluated and compared. The criterion can explain the location offset of the ring crack upon loading, as observed in various ceramics and glasses. It also predicts the ring crack initiation force upon contact loading, provided that surface compressive stresses, introduced during grinding or polishing processes, are taken into account. Furthermore, the stress–energy criterion may be employed to estimate the surface residual stress of ceramic parts, based on simple contact damage experiments.     

The peak-shift method for the description of structural relaxation in glassy materials: a critical review

Nowadays, the glass transition kinetics is most commonly described in terms of the Tool–Narayanaswamy–Moynihan (TNM) model. Evaluation of one of the most prominent features of the structural relaxation motions—the relaxation nonlinearity—was traditionally done using the peak-shift (PS) method. This paper introduces, for the first time, extensive testing of the PS method by means of theoretical simulations for all practically observable types of structural relaxation behavior and all types of glassy/amorphous materials (tested range of the glass transition temperatures: −55 to 1000°C; tested range of the relaxation activation energies: 300–1300 kJ⋅mol⁻¹). For the majority of types of structural relaxation behavior, the PS method tends to slightly overestimate the value of the TNM nonlinearity parameter x (by ∼ 0.05–0.10). In the specific cases of the highly linear behavior (↑ x) combined with a broad distribution of relaxation times, the PS method systematically vastly underestimates the value of x. A new, improved temperature program was proposed for the PS method, eliminating the major intrinsic drawback of the originally proposed version of the PS methodology. In addition, based on the comparison between the theoretically simulated and real-life experimental data, a new approach (based on the characteristic PS dependence shape) was introduced to estimate the width of the relaxation times distribution.     

Bacterial Dehydrogenases Facilitate Oxidative Inactivation and Bioremediation of Chloramphenicol

Antimicrobial resistance represents a major threat to human health and knowledge of the underlying mechanisms is therefore vital. Here, we report the discovery and characterization of oxidoreductases that inactivate the broad-spectrum antibiotic chloramphenicol via dual oxidation of the C3-hydroxyl group. Accordingly, chloramphenicol oxidation either depends on standalone glucose-methanol-choline (GMC)-type flavoenzymes, or on additional aldehyde dehydrogenases that boost overall turnover. These enzymes also enable the inactivation of the chloramphenicol analogues thiamphenicol and azidamfenicol, but not of the C3-fluorinated florfenicol. Notably, distinct isofunctional enzymes can be found in Gram-positive (e. g., Streptomyces sp.) and Gram-negative (e. g., Sphingobium sp.) bacteria, which presumably evolved their selectivity for chloramphenicol independently based on phylogenetic analyses. Mechanistic and structural studies provide further insights into the catalytic mechanisms of these biotechnologically interesting enzymes, which, in sum, are both a curse and a blessing by contributing to the spread of antibiotic resistance as well as to the bioremediation of chloramphenicol.     

Feasibility study on electrically conductive joining of MoSi2 electrodes for spark plugs

Despite the often outstanding functional as well as (high temperature-) mechanical properties of ceramics, their usage is often limited due to their inherent brittleness. This also compromises the joining with metals, which is often indispensable for engineering applications. In this context, electrically conductive ceramics like MoSi₂ are promising materials for the application as electrodes where high temperatures in harsh environments are present (e.g., in spark plugs for large gas engines). Due to the difficult joining of the respective materials, long-term experiments are thereby often still pending. In this work, adhesive bonding, brazing, tungsten inert gas-, and resistance welding were performed to evaluate their applicability for generating electrically conductive as well as mechanically reliable joints between MoSi₂ and Inconel 600, aiming to utilize MoSi₂ electrodes in spark plugs. Fractographic analyses are performed to understand cracks associated with the high (thermo-) mechanical stresses. Additionally, a finite element model was set up for a deeper understanding of the observed fracture behavior. While adhesive bonding is acceptable for short-term experiments at low temperatures, brazing and resistance welding may qualify for fast and reliable manufacturing of spark plugs with ceramic electrodes.     

Holistic Analysis of the Tribological Interfaces of an Axial Piston Pump – Focusing on the Pump Efficiency

Research work performed on an axial piston pump is shown in a holistic manner, analyzing each lubricating interface by linking their gap height and temperature behavior to the overall pump efficiency. The temperature field and dynamic fluid film height were measured in two of the three lubricating interfaces. This is the first time that the temperature fields and gap heights were simultaneously measured in two of the main three interfaces of an axial piston machine. For a deeper analysis of the measurement data, all gaps were simulated with a numerical tool which takes solid body deformation due to temperature and pressure loads into account. This unique combination of both extensive measurement data and sophisticated simulation resulted in novel trends that clarify the complex phenomena occurring in these hydrostatic fluid films.     

Coupling of N2O Decomposition and Ethylbenzene Dehydrogenation over γ-Al2O3-Supported Transition Metal Oxide Catalysts

Transition metal (Cr, Cu, Fe, Co and Ni) oxides supported on -alumina were characterized with respect to their textural parameters and reducibility and used as catalysts in decomposition of nitrous oxide and ethylbenzene (EB) dehydrogenation as well as coupling of both processes. High activity of -Al₂O₃ in N₂O decomposition coupled with EB dehydrogenation has been found. An increase in EB and N₂O conversion was observed when transition-metal-containing catalysts were used. The activity of catalysts depended on their reducibility. Maximum N₂O efficiency was observed for the Cr/-Al₂O₃ sample, whereas -Al₂O₃-supported Cu and Fe oxide systems showed about 50% efficiency of N₂O in the reaction. An influence of the molar ratio of N₂O/EB on activity and selectivity of the catalysts was found. An excess of N₂O resulted in an increase in CO₂ formation at nearly constant styrene yield.     

Synthesis and characterization of poly[2-(10-undecenoyloxy)ethyl methacrylate]

Summary By Schotten-Baumann's esterification of poly(2-hydroxyethyl methacrylate) with 10-undecenoyl chloride a new multimonomer - poly[2-(10-undecenoyloxy)ethyl methacrylate] was prepared. Based on the results of elemental analysis, FTIR, ¹H-NMR and ¹³C-NMR spectra, the structure of the multimonomer was proposed. The thermal properties of the multimonomer were studied by DSC and TG. The rate of disappearance of double bonds in the multimonomer during UV irradiation was examined in the solid state to obtain a crosslinked product. Received: 17 September 2001/Revised version: 5 February 2002/ Accepted: 7 March 2002     

Formation of Nanocrystalline Transition-Metal Ferrites inside a Silica Matrix

Nanocrystalline transition-metal ferrites were synthesized inside an amorphous silica matrix by the sol–gel method. The formation of spinel ferrites began above 400°C, giving fine particles of about 10 nm at 800°C. This is associated with a specific role of the silica matrix, which facilitates the diffusion of the reacting cations, enhancing the ferrite formation. Above 1000°C the MnFe₂O₄ and CuFe₂O₄ nanoparticles lost their fine nature. The dried gels and crystalline materials were characterized by X-ray diffraction, thermal, FTIR, and BET analyses as well as by high-resolution scanning transmission electron microscopy.