Composite materials for photovoltaics: A realistic aim?

Layer-type microcrystalline powders of WS₂, MoS₂, WSe₂ and MoSe₂, which were tested for photoeffects with contact free microwave conductivity measurements, were incorporated into a nanostructured TiO₂ matrix in an attempt to obtain macroscopic photocurrents. Even though only 10% of the microcrystals were found to be active in contact with an iodide/iodine solution, photocurrents of the order of 100 μA/cm² to 1 mA/cm² were measured. The photoelectrochemical behavior of microcrystals was studied with space resolved photocurrent and photovoltage measurement techniques and it was attempted to understand the mechanism of current generation via the TiO₂/microcrystal/electrolyte interaction. Critical and still unresolved problems are recognized to be the control and optimization of photoeffects in microcrystals and the adjustment of doping levels of the two material faces. Only small photopotentials could be observed up to now, probably due to an insufficient and inhomogeneous doping of microcrystals. More research will be needed to determine whether this strategy could lead to realistic photovoltaic systems.     

Food matrices – determination of odorant partition coefficients and application of models for their prediction

Foods are complex multi-component systems which are composed of volatile and non-volatile substances. The flavour profile of a food is an important criterion for the selection of our foodstuffs. The main objective of this study was the clarification of the complex relationships of the flavour release as a function of the composition of the food matrix at molecular level. Therefore the influence of matrix effects onto the odorants partition coefficients in oil–water model systems and a custard sample were investigated. The studies included a series of lactones, ester and alcohols (γ- and δ-octalactone, γ- and δ-nonalactone, γ- and δ-decalactone, ethyl hexanoate, 3-methyl-1-butanol and 2-phenylethanol). The partition coefficients were determined using static headspace gas chromatography (SH-GC). The results indicated that the custard/air partition coefficients of selected odorants are located between the water/air- and miglyol/air partition coefficients. Furthermore the mass transfer rates of selected odorants were investigated in custard- and milk powder–water samples. The values of the mass transfer rate were found higher in milk powder/water systems than in custard model. Nevertheless the results indicated that the viscosity of the matrix did not significantly influence the values of mass transfer rate of selected flavour compounds.     

Microbiological, biochemical and biogenic amine profiles of Terrincho cheese manufactured in several dairy farms

Terrincho is a Portuguese traditional cheese, bearing a protected denomination of origin (PDO) status, which is manufactured from raw ewes’ milk and ripened for a minimum period of 30 d. The objectives of this research effort were to characterize the microbiological and biochemical profiles of this cheese, manufactured in several dairy farms during the winter cheesemaking season (December through March), and establish tentative correlations between these profiles and formation of biogenic amines. For this goal, 29 cheeses from five batches, manufactured in as many dairy farms located throughout the PDO region, were analysed. The viable numbers of the total (mesophilic) microflora, enterococci, lactococci, lactobacilli, enterobacteria, staphylococci, pseudomonads, yeasts and moulds were determined by 30 d, following classical plate counting on specific media. Free amino acid and biogenic amine contents were determined by reverse-phase high-pressure liquid chromatography. The concentration of biogenic amines correlated well with microbial viable numbers, in both qualitative and quantitative terms; significant correlations were observed between enterococci and phenylethylamine (r=0.868, p<0.0001), and between lactococci and cadaverine (r=0.646, p=0.002) and tyramine (r=0.868, p<0.0001). On the other hand, 220 g of Terrincho cheese would have to be consumed at a given time if the threshold of worst case risk was to be attained, which appears unrealistic for a typically single-doses meal ingredient. This study has contributed to deepen the knowledge on the microbiological and biochemical features of a unique Portuguese cheese throughout ripening, and to rationalize its safe consumption in terms of biogenic amines.     

Atomic force microscopy study of the antibacterial effects of chitosans on Escherichia coli and Staphylococcus aureus

Chitosan has been reported to be a non-toxic, biodegradable antibacterial agent. The aim of this work was to elucidate the relationship between the molecular weight of chitosan and its antimicrobial activity upon two model microorganisms, one Gram-positive (Staphylococcus aureus) and one Gram-negative (Escherichia coli). Atomic force microscopy (AFM) imaging was used to obtain high-resolution images of the effect of chitosans on the bacterial morphology. The AFM measurements were correlated with viable cell numbers, which show that the two species reacted differently to the high- and low-molecular-weight chitosan derivatives. The images obtained revealed not only the antibacterial effects, but also the response strategies used by the bacteria; cell wall collapse and morphological changes reflected cell death, whereas clustering of bacteria appeared to be associated with cell survival. In addition, nanoindentation experiments with the AFM revealed mechanical changes in the bacterial cell wall induced by the treatment. The nanoindentation results suggested that despite little modification observed in the Gram-positive bacteria in morphological studies, cell wall damage had indeed occurred, since cell wall stiffness was reduced after chitooligosaccharide treatment.     

Mercury speciation in gypsums produced from flue gas desulfurization by temperature programmed decomposition

Temperature programmed decomposition was used to identify mercury (Hg) species in gypsum samples produced from flue gas desulfurization in two Spanish power stations (A and B). As stricter emission control/reduction policies, particularly those focusing on Hg, are being implemented, wet flue gas desulfurization (FGD) technologies used for the removal of SO₂ can result in the co-removal of highly-soluble oxidized Hg. The amount of Hg retained in FGD products may increase in the future if these units are optimized for co-capture. For this reason, it is important to identify the mercury species in FGD products not only to determine the potential risk when the wastes are finally disposed of, but also to understand the behaviour of mercury during combustion and therefore to improve the technologies for mercury removal. Different mercury species were identified in the gypsum samples. In power station A, HgS were the most probable Hg species, whereas in power station B the main compound was Hg halogenated compounds.     

Attaching Different Kinds of Proteinaceous Nanospheres to a Variety of Fabrics Using Ultrasound Radiation

The application of a rapid, non-destructive, cost-effective technique such as ultrasonic emulsification for the coating of different textiles was explored. The technical benefits for this research were the generation of multifunctional materials and their combinations through environmentally friendly processing technologies. We have shown for the first time that ultrasonic waves can be used to coat proteinaceous micro- and nanospheres (PM) of BSA (Bovine Serum Albumin) protein and casein on the surface of cotton and polyester (PE) fabrics. The creation and the anchoring of the microbubbles to the fabrics were performed by a one-step reaction, and the process is usually stopped after 3 min. The PM of bovine serum albumin (BSA) bonded to cotton and polyester fabrics has shown stability for ∼9 months. The PMs were shown to be attached more strongly to the polyester than to the cotton, and sustained stronger washing conditions on PE. The diameter of the BSA and the casein spheres on cotton was in the range of 0.8–1.0 μm, while on the PE it varied between 60 and 120 nm.     

Biological properties of iron oxide nanoparticles for cellular and molecular magnetic resonance imaging

Superparamagnetic iron-oxide particles (SPIO) are used in different ways as contrast agents for magnetic resonance imaging (MRI): Particles with high nonspecific uptake are required for unspecific labeling of phagocytic cells whereas those that target specific molecules need to have very low unspecific cellular uptake. We compared iron-oxide particles with different core materials (magnetite, maghemite), different coatings (none, dextran, carboxydextran, polystyrene) and different hydrodynamic diameters (20-850 nm) for internalization kinetics, release of internalized particles, toxicity, localization of particles and ability to generate contrast in MRI. Particle uptake was investigated with U118 glioma cells und human umbilical vein endothelial cells (HUVEC), which exhibit different phagocytic properties. In both cell types, the contrast agents Resovist, B102, non-coated Fe(3)O(4) particles and microspheres were better internalized than dextran-coated Nanomag particles. SPIO uptake into the cells increased with particle/iron concentrations. Maximum intracellular accumulation of iron particles was observed between 24 h to 36 h of exposure. Most particles were retained in the cells for at least two weeks, were deeply internalized, and only few remained adsorbed at the cell surface. Internalized particles clustered in the cytosol of the cells. Furthermore, all particles showed a low toxicity. By MRI, monolayers consisting of 5000 Resovist-labeled cells could easily be visualized. Thus, for unspecific cell labeling, Resovist and microspheres show the highest potential, whereas Nanomag particles are promising contrast agents for target-specific labeling.     

Synthetic Chain Terminators Off‐Load Intermediates from a Type I Polyketide Synthase

Modular biocatalysis is responsible for the generation of countless bioactive products and its mining remains a major focus for drug discovery purposes. One of the enduring hurdles is the isolation of biosynthetic intermediates in a readily‐analysed form. We prepared a series of nonhydrolysable pantetheine and N‐acetyl cysteamine mimics of the natural (methyl)malonyl extender units recruited for polyketide formation. Using these analogues as competitive substrates, we were able to trap and off‐load diketide and triketide species directly from an in vitro reconstituted type I polyketide synthase, the 6‐deoxyerythronolide B synthase 3 (DEBS3). The putative intermediates, which were extracted in organic solvent and characterised by LC‐HR‐ESI‐MS, are the first of their kind and prove that small‐molecule chain terminators can be used as convenient probes of the biosynthetic process.     

Modulation on C‐ and N‐Terminal Moieties of a Series of Potent and Selective Linear Tachykinin NK2 Receptor Antagonists

Herein we describe the synthesis of a series of new potent tachykinin NK₂ receptor antagonists by the modulation of the C‐ and N‐terminal moieties of ibodutant (MEN 15596, 1 ). The N‐terminal benzo[b]thiophene ring was replaced by different substituted naphthalenes and benzofurans, while further modifications were evaluated at the C‐terminal tetrahydropyran moiety. Most compounds demonstrated a high affinity for the human NK₂ receptor and high in vitro antagonist potency, indicating that a wide range of substituents at both termini can be incorporated in the molecule without detrimental effects on the interactions with the NK₂ receptor. Selected compounds were tested in vivo confirming their activity as NK₂ antagonists. In particular, after both iv and id administration to guinea pig, compound 61 b was able to antagonize NK₂‐induced colonic contractions with a potency and duration‐of‐action fully comparable to the reference compound 1 (MEN 15596, ibodutant).