Polystyrene and asphaltene micelles within blends with a bitumen of an SBS block copolymer and styrene and butadiene homopolymers

Using fluorescence microscopy, DSC and DMTA we have explored blends of a bitumen with a styrene-butadiene-styrene (SBS) block copolymer, and with blends of the bitumen with SBS and one or two homopolymers - a polystyrene and a poly(cis-butadiene). The SBS polymer was progressively replaced with quantities of the homopolymers both together in the proportions found in the block copolymer and then by each homopolymer separately. At low temperatures the blends are all softer than the bitumen itself, so the polymers plasticise the bitumen-rich phase, and above 50°C the blends' stiffness (E') falls below a plateau only when a critical proportion of the block copolymer has been replaced with the two homopolymers: this supports the idea of an extensive network created by the polystyrene-rich spherical microphases that is effective even when the polystyrene microphases have melted. In one polymer blend the stiffness rose as the temperature was raised above 100°C, suggesting the development of a mesophase based upon polybutadiene plus asphaltenes, in another E' was enhanced and E" remained constant as the temperature rose above 70°C, perhaps for a similar reason; in some loss process appeared and the stiffness fell as temperature rose; but in others a good part of the SBS was replaced by either polystyrene or polybutadiene without changing the appearance of a rubbery plateau, that is, without a diminution of the mechanical properties of the soft matter.

Melt-compounded nanocomposites of titanium dioxide atomic-layer-deposition-coated polyamide and polystyrene powders

Polyamide and polystyrene particles were coated with titanium dioxide films by atomic layer deposition (ALD) and then melt-compounded to form polymer nanocomposites. The rheological properties of the ALD-created nanocomposite materials were characterized with a melt flow indexer, a melt flow spiral mould, and a rotational rheometer. The results suggest that the melt flow properties of polyamide nanocomposites were markedly better than those of pure polyamide and polystyrene nanocomposites. Such behavior was shown to originate in an uncontrollable decrease in the polyamide molecular weight, likely affected by a high thin-film impurity content, as shown in gel permeation chromatography (GPC) and scanning electron microscope (SEM) equipped with an energy-dispersive spectrometer. Transmission electron microscope image showed that a thin film grew on both studied polymer particles, and that subsequent melt-compounding was successful, producing well dispersed ribbon-like titanium dioxide with the titanium dioxide filler content ranging from 0.06 to 1.12wt%. Even though we used nanofillers with a high aspect ratio, they had only a minor effect on the tensile and flexural properties of the polystyrene nanocomposites. The mechanical behavior of polyamide nanocomposites was more complex because of the molecular weight degradation. Our approach here to form polymeric nanocomposites is one way to tailor ceramic nanofillers and form homogenous polymer nanocomposites with minimal work-related risks in handling powder form nanofillers. However, further research is needed to gauge the commercial potential of ALD-created nanocomposite materials. Copyright (C) 2011 John Wiley & Sons, Ltd.

Contribution of process variables to the entrapment efficiency of propranolol hydrochloride within ethylcellulose microspheres prepared by the solvent evaporation method as evaluated using a factorial design

The effects of the process variables, pH of aqueous phase, rate of addition of organic, polymeric, drug-containing phase to aqueous phase, organic:aqueous phase volume ratio and aqueous phase temperature on the entrapment of propranolol hydrochloride in ethylcellulose (N4) microspheres prepared by the solvent evaporation method were examined using a factorial design. The observed range of drug entrapment was 1.43 +/- 0.02%w/w (pH 6, 25 degrees C, phase volume ratio 1:10, fast rate of addition) to 16.63 +/- 0.92%w/w (pH 9, 33 degrees C, phase volume ratio 1:10, slow rate of addition) which corresponded to mean entrapment efficiencies of 2.86 and 33.26, respectively. Increased pH, increased temperature and decreased rate of addition significantly enhanced entrapment efficiency. However, organic:aqueous phase volume ratio did not significantly affect drug entrapment. Statistical interactions were observed between pH and rate of addition, pH and temperature, and temperature and rate of addition. The observed interactions involving pH are suggested to be due to the abilities of increased temperature and slow rate of addition to sufficiently enhance the solubility of dichloromethane in the aqueous phase, which at pH 9, but not pH 6, allows partial polymer precipitation prior to drug partitioning into the aqueous phase. The interaction between temperature and rate of addition is due to the relative lack of effect of increased temperature on drug entrapment following slow rate of addition of the organic phase. In comparison to the effects of pH on drug entrapment, the contributions of the other physical factors examined were limited.

Antigen-specific IgA and IgG responses in calves inoculated intranasally with ovalbumin encapsulated in poly(DL-lactide-co-glycolide) microspheres

The immunogenicity of proteins encapsulated in poly(DL-lactide-co-glycolide) (PLG) microspheres has not been investigated to any extent in large animal models. In this study, IgG and IgA responses to ovalbumin (OVA), encapsulated in microspheres was investigated following intranasal inoculation into calves. Scanning electron microscopy and flow cytometric analysis demonstrated a uniform microsphere population with a diameter of <2.5 micrometers. Ovalbumin was released steadily from particles stored in PBS almost in a linear fashion, and after 4 weeks many particles showed cracks and fissures in their surface structure. Following intranasal inoculation of calves with different doses of encapsulated antigen, mean levels of ovalbumin-specific IgA were observed to increase steadily but significant differences in IgA levels (from the pre-inoculation level) were only observed following a second intranasal inoculation. With 0.5 and 1.0mg doses of antigen, ovalbumin-specific IgG was also detected in serum. Ovalbumin-specific IgA persisted in nasal secretions for a considerable period of time and were still detectable in four out of seven animals, 6 months after inoculation.

Studies in the use of magnetic microspheres for immunoaffinity extraction of paralytic shellfish poisoning toxins from shellfish

Paralytic shellfish poisoning (PSP) is a potentially fatal human health condition caused by the consumption of shellfish containing high levels of PSP toxins. Toxin extraction from shellfish and from algal cultures for use as standards and analysis by alternative analytical monitoring methods to the mouse bioassay is extensive and laborious. This study investigated whether a selected MAb antibody could be coupled to a novel form of magnetic microsphere (hollow glass magnetic microspheres, brand name Ferrospheres-N) and whether these coated microspheres could be utilized in the extraction of low concentrations of the PSP toxin, STX, from potential extraction buffers and spiked mussel extracts. The feasibility of utilizing a mass of 25 mg of Ferrospheres-N, as a simple extraction procedure for STX from spiked sodium acetate buffer, spiked PBS buffer and spiked mussel extracts was determined. The effects of a range of toxin concentrations (20-300 ng/mL), incubation times and temperature on the capability of the immuno-capture of the STX from the spiked mussel extracts were investigated. Finally, the coated microspheres were tested to determine their efficiency at extracting PSP toxins from naturally contaminated mussel samples. Toxin recovery after each experiment was determined by HPLC analysis. This study on using a highly novel immunoaffinity based extraction procedure, using STX as a model, has indicated that it could be a convenient alternative to conventional extraction procedures used in toxin purification prior to sample analysis.

The impacts of replacing air bubbles with microspheres for the clarification of algae from low cell-density culture

Dissolved Air Flotation (DAF) is a well-known coagulation-flotation system applied at large scale for microalgae harvesting. Compared to conventional harvesting technologies DAF allows high cell recovery at lower energy demand. By replacing microbubbles with microspheres, the innovative Ballasted Dissolved Air Flotation (BDAF) technique has been reported to achieve the same algae cell removal efficiency, while saving up to 80% of the energy required for the conventional DAF unit. Using three different algae cultures (Scenedesmus obliquus, Chlorella vulgaris and Arthrospira maxima), the present work investigated the practical, economic and environmental advantages of the BDAF system compared to the DAF system. 99% cells separation was achieved with both systems, nevertheless, the BDAF technology allowed up to 95% coagulant reduction depending on the algae species and the pH conditions adopted. In terms of floc structure and strength, the inclusion of microspheres in the algae floc generated a looser aggregate, showing a more compact structure within single cell alga, than large and filamentous cells. Overall, BDAF appeared to be a more reliable and sustainable harvesting system than DAF, as it allowed equal cells recovery reducing energy inputs, coagulant demand and carbon emissions. © 2014 Elsevier Ltd.

Multi-detection method for five common microalgal toxins based on the use of microspheres coupled to a flow-cytometry system

Freshwater and brackish microalgal toxins, such as microcystins, cylindrospermopsins, paralytic toxins, anatoxins or other neurotoxins are produced during the overgrowth of certain phytoplankton and benthic cyanobacteria, which includes either prokaryotic or eukaryotic microalgae. Although, further studies are necessary to define the biological role of these toxins, at least some of them are known to be poisonous to humans and wildlife due to their occurrence in these aquatic systems. The World Health Organization (WHO) has established as provisional recommended limit 1 μg of microcystin-LR per liter of drinking water. In this work we present a microsphere-based multi-detection method for five classes of freshwater and brackish toxins: microcystin-LR (MC-LR), cylindrospermopsin (CYN), anatoxin-a (ANA-a), saxitoxin (STX) and domoic acid (DA). Five inhibition assays were developed using different binding proteins and microsphere classes coupled to a flow-cytometry Luminex system. Then, assays were combined in one method for the simultaneous detection of the toxins. The IC₅₀'s using this method were 1.9 ± 0.1 μg L⁻¹ MC-LR, 1.3 ± 0.1 μg L⁻¹ CYN, 61 ± 4 μg L⁻¹ ANA-a, 5.4 ± 0.4 μg L⁻¹ STX and 4.9 ± 0.9 μg L⁻¹ DA. Lyophilized cyanobacterial culture samples were extracted using a simple procedure and analyzed by the Luminex method and by UPLC–IT-TOF-MS. Similar quantification was obtained by both methods for all toxins except for ANA-a, whereby the estimated content was lower when using UPLC–IT-TOF-MS. Therefore, this newly developed multiplexed detection method provides a rapid, simple, semi-quantitative screening tool for the simultaneous detection of five environmentally important freshwater and brackish toxins, in buffer and cyanobacterial extracts.

Zinc selenide nano- and microspheres via microwave-assisted ionothermal synthesis

Zinc selenide nanospheres were prepared from a diphenyl diselenide precursor and a range of chloro- and bromozincate(II) ionic liquids via a microwave-assisted ionothermal route; this is the first report on the use of microwave irradiation in combination with ionic liquids to prepare this material. The method is a time-efficient and a facile one-pot reaction to produce zinc(II) selenide nanomaterials. The product formation in the ionic liquids has been monitored using Raman spectroscopy. The products have been characterised using PXRD, SEM, EDX, photoluminescence and UV-VIS spectroscopy. Advantages of this new route, such as ease of solubilisation of all reactants into one phase at high concentration, the negligible vapour pressure irrespective of the reaction temperature, very fast reaction times, ease of potential scale-up and reproducibility are discussed.

Photocatalytic degradation of eleven microcystin analogues and nodularin by TiO2 coated glass microspheres

Microcystins and nodularin are toxic cyanobacterial secondary metabolites produced by cyanobacteria that pose a threat to human health in drinking water. Conventional water treatment methods often fail to remove these toxins. Advanced oxidation processes such as TiO2 photocatalysis have been shown to effectively degrade these compounds. A particular issue that has limited the widespread application of TiO2 photocatalysis for water treatment has been the separation of the nanoparticulate power from the treated water. A novel catalyst format, TiO2 coated hollow glass spheres (Photospheres™), is far more easily separated from treated water due to its buoyancy. This paper reports the photocatalytic degradation of eleven microcystin variants and nodularin in water using Photospheres™. It was found that the Photospheres™ successfully decomposed all compounds in 5 minutes or less. This was found to be comparable to the rate of degradation observed using a Degussa P25 material, which has been previously reported to be the most efficient TiO2 for photocatalytic degradation of microcystins in water. Furthermore, it was observed that the degree of initial catalyst adsorption of the cyanotoxins depended on the amino acid in the variable positions of the microcystin molecule. The fastest degradation (2 minutes) was observed for the hydrophobic variants (microcystin-LY, -LW, -LF). Suitability of UV-LEDs as an alternative low energy light source was also evaluated.

Biaxial Characterisation of Materials for Thermoforming and Blow Moulding

During free surface moulding processes such as thermoforming and blow moulding heated polymer materials are subjected to rapid biaxial deformation as they are drawn into the shape of a mould. In the development of process simulations it is therefore essential to be able to accurately measure and model this behaviour. Conventional uniaxial test methods are generally inadequate for this purpose and this has led to the development of specialised biaxial test rigs. In this paper the results of several programmes of biaxial tests conducted at Queen’s University are presented and discussed. These have included tests on high impact polystyrene (HIPS), polypropylene (PP) and aPET, and the work has involved a wide variety of experimental conditions. In all cases the results clearly demonstrate the unique characteristics of materials when subjected to biaxial deformation. PP draws the highest stresses and it is the most temperature sensitive of the materials. aPET is initially easier to form but exhibits strain hardening at higher strains. This behaviour is increased with increasing strain rate but at very high strain rates these effects are increasingly mollified by adiabatic heating. Both aPET and PP (to a lesser degree) draw much higher stresses in sequential stretching showing that this behaviour must be considered in process simulations. HIPS showed none of these effects and it is the easiest material to deform.