MoO2 Diffusion in Aluminosilicate Glass

A diffusion couple of an oxidized molybdenum disk and a glass cylinder was used to measure the solubiiity and effective binary diffusion coefficient of MoO₂ in a non-alkali aluminosilicate glass. At 1400°C, the solubility limit was 8.4 mol%; the value of the diffusion coefficient (4.1 × 10⁻¹⁶ m²/s) was significantly lower than that estimated from the Stokes-Einstein relation.     

Ditopic, flexible hydrazone-based building blocks with pendant 2,2′:6′,2′′-terpyridine metal-binding domains

The synthesis and characterization of three new bis(2,2′:6′,2′-terpyridine) (tpy) ligands containing different hydrazone spacers between the metal-binding domains are described. Treatment of 1,4-benzenedicarbaldehyde bis(2,2′:6′,2′′-terpyridin-4′-ylhydrazone) (1) with [(tpy)RuCl₃] in the presence of N-ethylmorpholine results in the formation of [(tpy)Ru(μ-1)Ru(tpy)]⁴⁺. Single crystal X-ray diffraction data for [(tpy)Ru(μ-1)Ru(tpy)][PF₆]₄·8MeCN confirm the ability of the hydrazone-based ligand to bridge two ruthenium(II) centres, providing proof-of-principle for the application of this class of flexible ligand in the design of coordination polymers.     

Supramolecular and nanochemistry

The following contributions describe various research activities of the Department of Chemistry, University of Basel in the area of nanochemistry and supramolecular chemistry.     

Starch-zein blends formed by shear flow

A newly in-house developed shearing device was used to explore the formation of new types of microstructures in concentrated starch-zein blends. The device allowed processing of the biopolymer blends under homogeneous, simple shear flow conditions. Water and glycerol were added as plasticizers. Different ratios (0-20% zein, dry basis) were used to study the influence of the matrix composition and processing conditions on the properties of the final material. The properties at large deformation were examined by tensile tests in two different directions (i.e. along the flow (∥) and in the vorticity (⊥) directions). The morphology of the blends observed by confocal scanning laser microscopy and field emission scanning electron microscopy showed that under shearless conditions, starch-zein formed a co-continuous blend. The application of shear transformed this structure into a dispersion, with zein as the dispersed phase. The size of the zein aggregates increased with zein concentration. A certain degree of anisotropy was found with the 10% zein blend at the highest shear rate applied . Here, the zein aggregates were slightly deformed along the shear flow (∥). Both microscopy and tensile tests indicated that the blends have no or weak adhesion between the zein and starch phases. The effect of zein particles on the mechanical properties followed a modified model used for particle-matrix materials with weak adhesion between the phases.     

Identification of trinucleotide repeat ligands with a FRET melting assay

DNA hairpin structures formed within a repeated tract might be a causative factor for triplet expansion observed in several debilitating diseases. We have designed and used a fluorescence resonance energy transfer (FRET) melting assay to screen for ligands that bind specifically to the CNG triplet repeats. Using this assay, we screened a panel of 33 chemicals that were previously designed to bind DNA or RNA secondary structures. Remarkably, we found that macrocyclic compounds, such as acridine dimers and trimers, exhibit interesting affinities and specificities for this motif.     

The role of support on the performance of platinum-based catalysts for the total oxidation of polycyclic aromatic hydrocarbons

A range of Pt supported catalysts have been evaluated for the total oxidation of naphthalene. Catalysts contained 0.5 wt% Pt on a range of supports (γ-Al₂O₃, TiO₂, SiO₂, SnO₂, and CeO₂₎. SiO₂ was the best support, the 0.5%Pt/SiO₂ catalyst showing a conversion to carbon dioxide of over 90% at 200 °C (100 vppm naphthalene, GHSV = 45,000 h⁻¹). The catalyst also showed a considerably higher activity (in the temperature range 100–175 °C) than a CeO₂ catalyst recently reported to be one of the most effective catalysts for the total oxidation of naphthalene. The high activity of the 0.5%Pt/SiO₂ catalyst has been attributed to the relatively low dispersion and relatively large size of Pt particles. Furthermore, due to the acidic and non-reducible nature of the SiO₂, platinum is expected to have a weak interaction with the support. XPS data identified the presence of Pt⁰ on the surface and this contributes to the high activity.     

Effects of Interface Roughness on Residual Stresses in Thermal Barrier Coatings

Using a newly developed object-oriented finite-element analysis method, both an actual microstructure and model microstructures of a plasma-sprayed thermal barrier coating system were numerically simulated to analyze the full-field residual stresses of this coating system. Residual stresses in the actual microstructure were influenced by both the irregular top-coat/bond-coat interface and cracks in the top coat. By treating the microcracked top coat as a more-compliant solid microstructure, the effects of the irregular interface on residual stresses were examined. These results then could be compared to results that have been obtained by analyzing a model microstructure with a sinusoidal interface, which has been considered by some earlier investigators.     

Inhibition of Autophagy Does Not Re-Sensitize Acute Myeloid Leukemia Cells Resistant to Cytarabine

Elevated activation of the autophagy pathway is currently thought to be one of the survival mechanisms allowing therapy-resistant cancer cells to escape elimination, including for cytarabine (AraC)-resistant acute myeloid leukemia (AML) patients. Consequently, the use of autophagy inhibitors such as chloroquine (CQ) is being explored for the re-sensitization of AraC-resistant cells. In our study, no difference in the activity of the autophagy pathway was detected when comparing AraC-Res AML cell lines to parental AraC-sensitive AML cell lines. Furthermore, treatment with autophagy inhibitors CQ, 3-Methyladenine (3-MA), and bafilomycin A1 (BafA1) did not re-sensitize AraC-Res AML cell lines to AraC treatment. However, in parental AraC-sensitive AML cells, treatment with AraC did activate autophagy and, correspondingly, combination of AraC with autophagy inhibitors strongly reduced cell viability. Notably, the combination of these drugs also yielded the highest level of cell death in a panel of patient-derived AML samples even though not being additive. Furthermore, there was no difference in the cytotoxic effect of autophagy inhibition during AraC treatment in matched de novo and relapse samples with differential sensitivity to AraC. Thus, inhibition of autophagy may improve AraC efficacy in AML patients, but does not seem warranted for the treatment of AML patients that have relapsed with AraC-resistant disease.     

The Importance of Therapeutically Targeting the Binary Toxin from Clostridioides difficile

Novel therapeutics are needed to treat pathologies associated with the Clostridioides difficile binary toxin (CDT), particularly when C. difficile infection (CDI) occurs in the elderly or in hospitalized patients having illnesses, in addition to CDI, such as cancer. While therapies are available to block toxicities associated with the large clostridial toxins (TcdA and TcdB) in this nosocomial disease, nothing is available yet to treat toxicities arising from strains of CDI having the binary toxin. Like other binary toxins, the active CDTa catalytic subunit of CDT is delivered into host cells together with an oligomeric assembly of CDTb subunits via host cell receptor-mediated endocytosis. Once CDT arrives in the host cell’s cytoplasm, CDTa catalyzes the ADP-ribosylation of G-actin leading to degradation of the cytoskeleton and rapid cell death. Although a detailed molecular mechanism for CDT entry and host cell toxicity is not yet fully established, structural and functional resemblances to other binary toxins are described. Additionally, unique conformational assemblies of individual CDT components are highlighted herein to refine our mechanistic understanding of this deadly toxin as is needed to develop effective new therapeutic strategies for treating some of the most hypervirulent and lethal strains of CDT-containing strains of CDI.     

Success factors of energy performance contracting (EPC) for sustainable building energy efficiency retrofit (BEER) of hotel buildings in China

Hotel building is a type of high-energy-consuming building and most existing hotel buildings need energy efficiency improvement in China. Energy performance contracting (EPC) is considered a win−win mechanism to organize building energy efficiency retrofit (BEER) project. However, EPC mechanism has been introduced into China relatively recently and many EPCs have not been successful in building energy efficiency retrofit projects. This research aims to develop a set of critical success factors (CSFs) of EPC for sustainable energy efficiency retrofit (BEER) of hotel buildings in China. Semi-structured interviews and a questionnaire survey with practitioners and other professionals were conducted. The findings reveal the relative importance of the 21 number of identified success factors. In order to explore the underlying relationship among the identified critical success factors (CSFs), factor analysis method was adopted for further investigation, which leads to grouping the 21 identified CSFs into six clusters. These are (1) project organization process, (2) EPC project financing for hotel retrofit, (3) knowledge and innovation of EPC, sustainable development (SD), and M&V, (4) implementation of sustainable development strategy, (5) contractual arrangement, and (6) external economic environment. Finally, several relevant policies were proposed to implement EPC successfully in sustainable BEER in hotel buildings.