Compatibilisation of PPE/SAN blends by triblock terpolymers: Correlation between block terpolymer composition, morphology and properties

Immiscible blends of poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and poly(styrene-co-acrylonitrile) (SAN) with a weight composition of 60/40 were compatibilised by polystyrene-block-polybutadiene-block-poly(methyl methacrylate) triblock terpolymers (SBM) using a two-stage melt-processing approach. In order to investigate the influence of the SBM composition on the compatibilisation efficiency, the block lengths of the triblock terpolymers were systematically varied. The resulting morphological features of the blend systems as function of SBM composition and processing parameters are correlated with the resulting thermal and thermo-mechanical properties. In the ideal case, SBM should be located at the interface as PS is miscible with PPE while PMMA is miscible with SAN. The elastomeric middle block as an immiscible component should remain at the interface. This particular morphological arrangement is known as the ‘raspberry morphology’. A detailed TEM analysis of the blend morphologies following initial extrusion-compounding revealed a high compatibilisation efficiency of the SBM types with equal lengths of the end blocks and, furthermore, the desired raspberry morphology was achieved. In contrast, high PS contents in comparison to the other blocks led to a pronounced micelle formation in the PPE phase. Further evaluation of the blend structures following injection-moulding indicated that the morphologies remain relatively stable during this second melt-processing step. A detailed thermal analysis of all blend systems supports the interpretation of the observed morphological features. The fundamental correlation between SBM composition and blend morphology established in this study opens the door for the controlled development of interfacial properties of such compatibilised PPE/SAN blends during melt-processing.     

Manganese ferrite-polyaniline hybrid materials: Electrical and magnetic properties

Magnetic MnFe₂O₄ nanopowders were synthesized by an original solvothermal method in the absence and in the presence of tetra-n-butylammonium bromide (TBAB) and Tween 80 (TW) as surfactants. Manganese ferrite/polyaniline (PANI) hybrid materials were synthesized by in situ polymerization of aniline on the surface of MnFe₂O₄ using ammonium persulfate as oxidant. The purpose of the study was to investigate the influence of the two surfactants on the properties of the MnFe₂O₄ powders and of their composites with PANI. The specific surface area, the cumulative surface area of pores and the cumulative volume of pores are influenced by the nature of surfactant in case of MnFe₂O₄ powders and are higher by comparison to those of the MnFe₂O₄/PANI hybrid materials. The values of saturation magnetization in case of MnFe₂O₄ powders are higher than those of the hybrid materials and are not influenced by the surfactant nature. These features revealed that MnFe₂O₄ powders can be efficiently used as adsorbents for the purification of wastewaters. The values of the electrical conductivity of the composites exhibit a significant increase in comparison to the MnFe₂O₄ powders and depend on the surfactant nature. The highest value of electrical conductivity was achieved by the composite obtained using Tween 80 as surfactant (σ_DC = 54.5·10^?5S?m^?1) which was close to that of PANI (σ_DC = 61.2·10^?5 S?m^?1). The fact that the magnetic and electric properties of the synthesized MnFe₂O₄/PANI composites can be changed by design, demonstrate the high potential of these materials to be used in magneto-electric applications.     

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.     

Transmuting performance on manufacturing dimensions into business performance: An exploratory analysis of efficiency using DEA

This research examines efficiency in the transformation of performance on manufacturing competitive dimensions into business performance in the automotive supplier industry. Specifically, the study explores efficiency produced from data envelopment analysis (DEA) using cost, quality, time, flexibility and innovativeness performance as inputs and return on investment (ROI) and return on assets (ROA) as outputs. First tier suppliers to the 'Big 3' in North America were sampled. The 51 suppliers were categorized into three groups (high, medium and low) based on their efficiency. No significant group differences in quality, time, flexibility and innovativeness performance were found, but a significant difference does exist for cost. The results were further investigated by testing between-group differences for various cost reduction programmes, thereby identifying the levers and benchmarks for improving low efficiency firms.     

Thioarsenate transformation by filamentous microbial mats thriving in an alkaline, sulfidic hot spring

Thioarsenates dominate arsenic speciation in sulfidic geothermal waters, yet little is known about their fate in the environment. At Conch Spring, an alkaline hot spring in Yellowstone National Park, trithioarsenate transforms to arsenate under increasingly oxidizing conditions along the drainage channel, accompanied by an initial increase, then decrease of monothioarsenate and arsenite. On-site incubation tests were conducted using sterile-filtered water with and without addition of filamentous microbial mats from the drainage channel to distinguish the role of abiotic and biotic processes for arsenic species transformation. Abiotically, trithioarsenate was desulfidized to arsenate coupled to sulfide oxidation. Monothioarsenate, however, was inert. Biotic incubations proved that the intermediate accumulation of arsenite in the drainage channel is microbially catalyzed. In the presence of sulfide, microbially enhanced sulfide oxidation coupled to reduction of arsenate to arsenite could simply enhance abiotic desulfidation of trithioarsenate and potentially also monothioarsenate. However, we were also able to show, in sulfide-free medium, direct microbial transformation of monothioarsenate to arsenate. Some arsenite formed intermediately, which was subsequently also microbially oxidized to arsenate. This study is the first evidence for microbially mediated thioarsenate species transformation by (hyper)thermophilic prokaryotes.     

Polymeric vesicles: from drug carriers to nanoreactors and artificial organelles

One strategy in modern medicine is the development of new platforms that combine multifunctional compounds with stable, safe carriers in patient-oriented therapeutic strategies. The simultaneous detection and treatment of pathological events through interactions manipulated at the molecular level offer treatment strategies that can decrease side effects resulting from conventional therapeutic approaches. Several types of nanocarriers have been proposed for biomedical purposes, including inorganic nanoparticles, lipid aggregates, including liposomes, and synthetic polymeric systems, such as vesicles, micelles, or nanotubes. Polymeric vesicles--structures similar to lipid vesicles but created using synthetic block copolymers--represent an excellent candidate for new nanocarriers for medical applications. These structures are more stable than liposomes but retain their low immunogenicity. Significant efforts have been made to improve the size, membrane flexibility, and permeability of polymeric vesicles and to enhance their target specificity. The optimization of these properties will allow researchers to design smart compartments that can co-encapsulate sensitive molecules, such as RNA, enzymes, and proteins, and their membranes allow insertion of membrane proteins rather than simply serving as passive carriers. In this Account, we illustrate the advances that are shifting these molecular systems from simple polymeric carriers to smart-complex protein-polymer assemblies, such as nanoreactors or synthetic organelles. Polymeric vesicles generated by the self-assembly of amphiphilic copolymers (polymersomes) offer the advantage of simultaneous encapsulation of hydrophilic compounds in their aqueous cavities and the insertion of fragile, hydrophobic compounds in their membranes. This strategy has permitted us and others to design and develop new systems such as nanoreactors and artificial organelles in which active compounds are simultaneously protected and allowed to act in situ. In recent years, we have created a variety of multifunctional, proteinpolymersomes combinations for biomedical applications. The insertion of membrane proteins or biopores into the polymer membrane supported the activity of co-encapsulated enzymes that act in tandem inside the cavity or of combinations of drugs and imaging agents. Surface functionalization of these nanocarriers permitted specific targeting of the desired biological compartments. Polymeric vesicles alone are relatively easy to prepare and functionalize. Those features, along with their stability and multifunctionality, promote their use in the development of new theranostic strategies. The combination of polymer vesicles and biological entities will serve as tools to improve the observation and treatment of pathological events and the overall condition of the patient.     

Modulation of Aphid Alarm Pheromone Emission of Pea Aphid Prey by Predators

Recent studies on animal alarm signaling have shown that alarm calls generally are not uniform, but may vary depending on the type and intensity of threat. While alarm call variability has been studied intensively in birds and mammals, little is known about such variation in insects. We investigated variability in alarm signaling in aphids, group-living insect herbivores. Under attack, aphids release droplets containing a volatile alarm pheromone, (E)-β-farnesene (EBF), that induces specific escape behavior in conspecifics. We used a handheld gas chromatograph (zNose?), which allows real-time volatile analysis, to measure EBF emission by pea aphids, Acyrthosiphon pisum, under attack from different predators, lacewing or ladybird larvae. We demonstrate that aphid alarm signaling is affected by the predator species attacking. Ladybirds generally elicited smaller EBF emission peaks and consumed aphids more quickly, resulting in lower total EBF emission compared to lacewing attacks. In 52 % of the replicates with lacewings and 23 % with ladybirds, no EBF was detectable in the headspace, although aphids secreted cornicle droplets after attack. We, therefore, examined EBF amounts contained in these droplets and the aphid body. While all aphid bodies always contained EBF, many secreted droplets did not. Our experiments show that alarm signaling in insects can be variable, and both the attacker as well as the attacked may affect alarm signal variation. While underlying mechanisms of such variation in aphid-predator interactions need to be investigated in more detail, we argue that at least part of this variation may be adaptive for the predator and the aphid.