Gas Responsive Nanoswitch: Copper Oxide Composite for Highly Selective H2S Detection

A nanocomposite material based on copper(II) oxide (CuO) and its utilization as a highly selective and stable gas‐responsive electrical switch for hydrogen sulphide (H₂S) detection is presented. The material can be applied as a sensitive layer for H₂S monitoring, e.g., in biogas gas plants. CuO nanoparticles are embedded in a rigid, nanoporous silica (SiO₂) matrix to form an electrical percolating network of low conducting CuO and, upon exposure to H₂S, highly conducting copper(II) sulphide (CuS) particles. By steric hindrance due to the silica pore walls, the structure of the network is maintained even though the reversible reaction of CuO to CuS is accompanied by significant volume expansion. The conducting state of the percolating network can be controlled by a variety of parameters, such as temperature, electrode layout, and network topology of the porous silica matrix. The latter means that this new type of sensing material has a structure‐encoded detection limit for H₂S, which offers new application opportunities. The fabrication process of the mesoporous CuO@SiO₂ composite as well as the sensor design and characteristics are described in detail. In addition, theoretical modeling of the percolation effect by Monte‐Carlo simulations yields deeper insight into the underlying percolation mechanism and the observed response characteristics.     

Observation of Exchange Interaction in Iron(II) Spin Crossover Molecules in Contact with Passivated Ferromagnetic Surface of Co/Au(111)

Spin crossover (SCO) complexes sensitively react on changes of the environment by a change in the spin of the central metallic ion making them ideal candidates for molecular spintronics. In particular, the composite of SCO complexes and ferromagnetic (FM) surfaces would allow spin-state switching of the molecules in combination with the magnetic exchange interaction to the magnetic substrate. Unfortunately, when depositing SCO complexes on ferromagnetic surfaces, spin-state switching is blocked by the relatively strong interaction between the adsorbed molecules and the surface. Here, the Fe(II) SCO complex [Fe^II(Pyrz)₂] (Pyrz = 3,5-dimethylpyrazolylborate) with sub-monolayer thickness in contact with a passivated FM film of Co on Au(111) is studied. In this case, the molecules preserve thermal spin crossover and at the same time the high-spin species show a sizable exchange interaction of > 0.9 T with the FM Co substrate. These observations provide a feasible design strategy in fabricating SCO-FM hybrid devices.     

Occurrence, sources, and fate of benzothiazoles in municipal wastewater treatment plants

A set of six benzothiazoles was determined in effluents of three municipal wastewater treatment plants. Total concentrations of benzothiazoles ranged from 1.9 to 6.7 microg/ L, with benzothiazole-2-sulfonate (BTSA) being most prominent (35 - 70%), followed by benzothiazole, 2-hydroxybenzothiazole, and 2-methylthi benzothiazole (MTBT). The removal of benzothiazoles in tertiary municipal wastewater treatment was investigated in more detail in one of the plants during two sampling periods of several weeks. Total benzothiazole concentration decreased by 5-28% only. This very limited removal was primarily due to BTSA and MTBT that were either hardly removed or even increased in concentration. In street runoff benzothiazoles exceeded the wastewater concentrations by 1 order of magnitude, showing that surface runoff can be a significant source of benzothiazole emission. In household wastewater total concentrations were in the range of 50-80% of that found in municipal wastewater. These investigations outline that benzothiazoles, a class of polar and biologically active industrial chemicals, are regularly released with treated municipal wastewater and exhibit a considerable lifetime in surface waters.     

Environmental influences on the partitioning and diffusion of hydrophobic organic contaminants in microbial biofilms

A biofilm reactor was used to investigate kinetic and thermodynamic aspects of the sorption of polycyclic aromatic hydrocarbons (PAH) as model compounds for hydrophobic organic contaminants (HOC) to intact microbial biofilms. Effective diffusion coefficients are in the range of 10(-10) cm2 x s(-1) resulting in equilibration times of more than 3 days for a biofilm of 100 microm thickness. Diffusion in the biofilm was strongly temperature-dependent and increased by a factor of 3 (phenanthrene) to 6 (fluoranthene, pyrene) between 5 and 35 degrees C. Drying and rewetting of the biofilm as well as the inclusion of Ca2+ ions and of humic acids all strengthened the biofilm rigidity and slowed down the diffusion of PAH. The later two factors also influenced the thermodynamics of the process as they supported the partitioning of PAH into the biofilm. Humic acid inclusion from solution into the biofilm illustrates that a microbial biofilm can act as a primer allowing for the buildup of a particulate organic phase from dissolved organic matter. PAH metabolites (3-hydroxy-phenanthrene and 1-hydroxy-2-naphthoic acid) showed lower partition coefficients as compared to their parent compounds and 3-hydroxy-phenanthrene also showed a higher diffusion constant, indicating that these transformation products would be easily released into the water phase upon formation during PAH biodegradation in a biofilm. These results allow the quantification of the influence of environmental conditions on a biofilm's function as a sink or as a diffusion barrier for PAH from aqueous solution, and they indicate the importance of kinetic aspects of this partitioning process.     

Antibiotic resistance of coagulase-negative staphylococci associated with food and used in starter cultures

The resistance of 330 coagulase-negative staphylococci (CNS) associated with food or used in starter cultures and belonging to the species Staphylococcus carnosus, Staphylococcus condimenti, Staphylococcus piscifermentans, Staphylococcus equorum, Staphylococcus succinus and Staphylococcus xylosus, against 21 antibiotics was determined using the disk diffusion method. The incidence and number of resistances was found to be species and source of isolation dependent. Most strains of S. equorum (63%), S. succinus (90%) and S. xylosus (95%) exhibited resistances against up to seven antibiotics, whereas only few strains of S. carnosus (12%) and S. piscifermentans (27%) were antibiotic resistant. Resistances to lincomycin, penicillin, fusidic acid, oxacillin, ampicillin and tetracycline were predominant. Among strains of S. xylosus, the incidence of resistance ranged from 22% for tetracycline up to 69% for penicillin. Concerning the source of isolation, resistances were often determined in strains of S. equorum, S. succinus and S. xylosus isolated from cheese (87%) and sausage (83%), and strains of S. xylosus obtained from meat starter cultures (93%). Remarkably, all CNS were sensitive to the clinically important antibiotics chloramphenicol, clindamycin, cotrimoxazol, gentamicin, kanamycin, linezolid, neomycin, streptomycin, synercid and vancomycin. The phenotypic resistances to ss-lactam antibiotics, lincomycin and tetracycline were verified by PCR amplification and could be traced back to the genes blaZ, lnuA and tetK, respectively. This study permitted a comprehensive insight into the incidence of antibiotic resistances in food-associated CNS.     

Inhibition of sickle beta-chain (betaS)-dependent polymerization by nonhuman alpha-chains. A superinhibitory mouse-horse chimeric alpha-chain

Horse alpha-chain inhibits sickle beta-chain-dependent polymerization; however, its inhibitory potential is not as high as that of mouse alpha-chain. Horse alpha-(1-30) and alpha-(31-141) segments make, respectively, minor and major contributions to the inhibitory potential of horse alpha-chain. The sum of the inhibitory potential of the two segments does not account for the inhibitory potential of the full-length horse alpha-chain. Although the polymerization inhibitory potential of horse alpha-chain is lower than mouse alpha-chain, the inhibitory potential of horse alpha-(31-141) is comparable to that of mouse alpha-(31-141). When mouse alpha-(1-30) is stitched to horse alpha-(31-141), the product is a chimeric alpha-chain with an inhibitory potential greater than mouse alpha-chain. In contrast, the stitching of horse alpha-(1-30) with mouse alpha-(31-141) had no additional inhibitory potential. Molecular modeling studies of HbS containing the mouse-horse chimeric alpha-chain indicate altered side-chain interactions at the alpha1beta1 interface when compared with HbS. In addition, the AB/GH corner perturbations facilitate a different stereochemistry for the interaction of the epsilon-amino group of Lys-16(alpha) with the beta-carboxyl group of Asp-116(alpha), resulting in a decrease in the accessibility of the side chain of Lys-16(alpha) to the solvent. Based on molecular modeling, we speculate that these perturbations by themselves, or in synergy with the altered conformational aspects of the alpha1beta1 interactions, represent the molecular basis of the superinhibitory potential of the mouse-horse chimeric alpha-chains.     

Influence of the temperature profile in the interface on the bond strength of polyamide–polyurethane two‐component tensile bars

Two‐component tensile bars with polyamide 6 (PA) and thermoplastic polyurethane (TPU) unmodified and modified with 4,4′‐diphenylmethane diisocyanate (MDI) have been investigated. It is known that the bond strength of PA/TPU tensile bars can increase by about 50% if MDI‐modified polyurethane is applied. The subject of these studies is the analysis of the influence of the mass temperatures on the bond strength. The mass temperatures of the first and second injection process and the delay time between the first and second injection processes determine the temperature gradient in the interface at the moment of the second injection. There is an increase in the bond strength when there is an increasing temperature gradient; therefore, the mass temperature of the first component at the delay time has to be lower than the mass temperature of the second component. The temperature gradient can be used as a measure of the thermal annealing of the first component near the interface during the heat transfer from the second component. It can be concluded that effective thermal annealing causes an increase in the bond strength. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4297–4305, 2006     

Influence of sputter deposition parameters on the properties of tunable barium strontium titanate thin films for microwave applications

Barium strontium titanate (BST) thin films are studied with respect to their application as tunable dielectric at microwave frequencies. BST thin films are deposited by means of radio-frequency magnetron sputtering on platinized Si substrates. The substrate to target distance during sputter deposition is varied and the effect on structure, topology, composition and electronic properties is monitored using X-ray diffraction, atomic force microscopy, Rutherford backscattering spectrometry and X-ray photoelectron spectroscopy. These findings are related to the dielectric measurements, which are carried out at 1 MHz and in the microwave range up to 8 GHz using metal-insulator-metal structures with Pt electrodes. For further device evaluation, leakage current measurements are carried out. Changing the process parameter strongly affects the composition of the films. The results emphasize the possibility for enhancing the microwave properties by fine-tuning of the chosen process parameter.     

A kinetic study of Am(III)/humic colloid interactions

The interaction kinetics of the Am(III) ion with aquatic humic colloids is investigated under near-natural conditions by column experiments with a sandy aquifer sample rich in humic substancesforthe appraisal of the migration behavior of Am. The association and dissociation kinetics of the Am ion onto and from humic colloids control the migration of colloid-borne Am. As the contact time between Am and humic colloids prior to introduction into a column is increased, the mobility of colloid-borne Am is enhanced and hence the recovery of Am in the effluent increases. On the other hand, an increase of the migration time and residence time in column, respectively, reduces the Am recovery. Considering these experimental results a refined version of the kinetic model KICAM (Kinetically Controlled Availability Model), which suggests different Am binding modes with humic colloids, was developed. Applying KICAM it is possible to predict static and dynamic experiments affected by the kinetically controlled Am/humic colloid interactions over the range of 1 h up to several months. However, to apply these experimental results to long-term conditions, the Am binding scheme as proposed in KICAM needs to be verified. This paper provides, therefore, a basis for a better understanding of the colloid-borne Am migration in porous aquifer systems.     

Microwave treatment of dietary gelatin does not generate cis-4-hydroxy-l-proline, an inhibitor of collagen biosynthesis

Aqueous solutions (5?g/100?ml) of commercial preparations of (a) an enzymatic partial hydrolysate of gelatin and (b) type A gelatin were subjected to threefold heating to boiling in a domestic microwave oven at 750?W and to conventional heating. Then samples were totally hydrolyzed (6?M hydrochloric acid, 110??°C, 24?h) and investigated for the presence of eight possible stereoisomers of 3- and 4-hydroxyproline (Hyp) using capillary gas chromatography. Amino acids were analyzed as N(O)-trifluoroacetyl 2-propyl esters on Chirasil-l-Val and detected by selected ion monitoring mass spectrometry. Blanks of (a) and (b) were analyzed in parallel. Relative amounts of 5.0±0.2% cis-4-d-Hyp were generated from native trans-4-l-Hyp as a result of total hydrolysis in all samples and independent of previous treatment. Notably, neither cis-3-l-Hyp nor cis-4-l-Hyp could be detected in either of the gelatin samples. Thus a report on the generation of antifibrotic and therefore potentially hazardous cis-3-l-Hyp and cis-4-l-Hyp from protein-bonded native trans-3-l-Hyp and trans-4-l-Hyp on microwave heating of infant formulae could not be confirmed.