Tripodal amido complexes: molecular "claws" in main group and transition metal chemistry

The chemistry of transition metal amides has received new impetus in recent years due to the systematic exploitation of the amido function [NR(2)](-) in ligand design. A class of 3-fold symmetrical tripodal amido ligands has proved to be a valuable tool in the stabilization of early transition metal and main group metal complexes and complex fragments. Moreover, promising strategies for their use as chemical reagents and homogeneous catalysts have been developed. An overwiew of the current state of this field is given and the potential for further development will be highlighted.     

Biosynthesis of zinc oxide nanoparticles by petals extract of Rosa indica L., its formulation as nail paint and evaluation of antifungal activity against fungi causing onychomycosis

Aim: The authors report the biological synthesis of zinc oxide nanoparticles (ZnO‐NPs) from the petals extract of Rosa indica L. (rose). Its efficacy was evaluated against two dermatophytes: namely: Trichophyton mentagrophytes and Microsporum canis which cause onychomycosis. The activity of antibiotics against the tested dermatophytes was enhanced, when evaluated in combination with ZnO‐NPs. Methods and results: The synthesised ZnO‐NPs were preliminary detected by using ultraviolet UV visible spectroscopy, which showed specific absorbance. The ZnO‐NPs were further characterised by nanoparticle tracking analysis (NTA), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X‐ray diffraction and Zetasizer. Moreover, nanoparticles containing nail paint (nanopaint) was formulated and its antifungal activity was also assessed against T. mentagrophytes and M. canis. ZnO‐NPs and formulated nanopaint containing ZnO‐NPs, both showed significant antifungal activity. The maximum activity was noted against M. canis and lesser against T. mentagrophytes. Minimum inhibitory concentration of ZnO‐NPs was also determined against the dermatophytes causing onychomycosis infection. Conclusion: ZnO‐NPs can be utilised as a potential antifungal agent for the treatment of onychomycosis after more experimental trials.Inspec keywords: diseases, zinc compounds, nanoparticles, nanofabrication, antibacterial activity, microorganisms, nanomedicine, ultraviolet spectra, visible spectra, Fourier transform infrared spectra, transmission electron microscopy, X‐ray diffraction, biomedical materials, patient treatmentOther keywords: zinc oxide nanoparticle biosynthesis, Rosa indica L petals extract, nail paint, antifungal activity evaluation, dermatophyte, Trichophyton mentagrophytes, Microsporum canis, antibiotics activity, ultraviolet‐visible spectroscopy, nanoparticle tracking analysis, Fourier transform infrared spectroscopy, transmission electron microscopy, X‐ray diffraction, zetasizer, antifungal agent, onychomycosis treatment     

Biogenic copper nanoparticles promote the growth of pigeon pea (Cajanus cajan L.)

Environmental pollution and toxicity have been increasing due to the overuse of chemical fertilisers, which has encouraged nanotechnologists to develop eco‐friendly nano‐biofertilisers. The authors demonstrated the effect of biogenic copper nanoparticles (CuNPs) on the growth of pigeon pea (Cajanus cajan L.). The UV–visible analysis showed absorbance at 615 nm. Nanoparticle tracking and analysis revealed particle concentration of 2.18 × 10⁸ particles/ml, with an average size of 33 nm. Zeta potential was found to be −16.7 mV, which showed stability. X‐ray diffraction pattern depicted the face centred cubic structure of CuNPs; Fourier transform infrared spectroscopy demonstrated the capping due to acidic groups, and transmission electron micrograph showed nanoparticles with size 20–30 nm. The effect of CuNPs (20 ppm) on plant growth was studied, for the absorption of CuNPs by plants on photosynthesis, which was evaluated by measuring chlorophyll a fluorescence using Handy‐Plant Efficiency Analyser. CuNPs treatment showed a remarkable increase in height, root length, fresh and dry weights and performance index of seedlings. The overall growth of plants treated with CuNPs after 4 weeks was recorded. The results revealed that inoculation of CuNPs contribute growth and development of pigeon pea due to growth promoting activity of CuNPs.Inspec keywords: pollution, toxicology, nanotechnology, cropsOther keywords: biogenic copper nanoparticles, pigeon pea, Cajanus cajan L, environmental pollution, toxicity, chemical fertilisers, nanotechnologists, eco‐friendly nano‐biofertilisers, cash crop, UV‐visible analysis, nanoparticle tracking, zeta potential, X‐ray diffraction pattern, Fourier transform infrared spectroscopy, acidic groups, transmission electron micrograph, photosynthesis, chlorophyll, fluorescence, Handy‐Plant Efficiency Analyser, performance index     

Improved statistics of sub-mesoscale eddies in the Baltic Sea retrieved from SAR imagery

In the present article the spatio-temporal distribution of sub-mesoscale eddies seen in Envisat Advanced Synthetic Aperture Radar (ASAR) imagery of the Baltic Sea is discussed. A total of 1250 ASAR images acquired between 2009 and 2011 form the basis of our studies and show imprints of almost 7000 sub-mesoscale eddies. Since the visibility of vortical structures in synthetic aperture radar (SAR) imagery significantly depends on the near-surface wind speed, wind data from a numerical model of the Baltic Sea were additionally used to obtain improved eddy statistics. Seasonally averaged fields of near-surface wind speed, surface currents, sea surface temperature (SST), and SST gradient were also analysed in order to reveal the role of these hydrophysical parameters in the observed spatial and temporal variation of sub-mesoscale eddies.     

Control of Variation by Reward Probability.

Two bar-press experiments with rats tested the rule that reducing expectation of reward increases the variation from which reward selects. Experiment 1 used a discrete-trial random-interval schedule, with trials signaled by light or sound. One signal always ended with reward; the other signal ended with reward less often. The 2 signals were randomly mixed. Bar-press duration (how long the bar was held down) varied more during the signal with the lower probability of reward. Experiment 2 closely resembled Experiment 1 but used a random-ratio schedule rather than a random-interval schedule. Again, bar-press duration varied more during the signal with the lower probability of reward. The results support the rule--the first well-controlled comparisons to do so. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Clean seas: a North Sea test site

The Clean Seas project focused on the role that existing Earth observing satellites might play in monitoring marine pollution. Results are presented here from August 1997, for the North Sea test site, using sea surface temperature (SST), colour and synthetic aperture radar (SAR) images in conjunction with a hydrodynamic model. There was good correlation between data sources, e.g. between SST and ERS-2 SAR images. Both datasets showed the development of fine plume structures close to the Rhine outflow, apparently associated with the outflow, and possibly caused by tidal pulsing of the Rhine Plume.

The model reproduced general temperature and sediment distributions well, but fine structures were not reproduced. Model sediment distribution patterns were verified using ‘chlorophyll concentration’ data from colour sensors, representative of sediment concentration in turbid water. In conjunction with the visible channels of the Advanced Very High Resolution Radiometer and Along-Track Scanning Radiometer, they give an uncalibrated measure of the sediment load. The model gives a more complete picture of the temporal dispersion of the Rhine Plume over time than is evident from the remotely sensed data alone.     

A sorption rate hypothesis for the increase in H2 permeability of palladium-silver (Pd-Ag) membranes caused by air oxidation

Hydrogen permeation measurements were performed at 300 °C for 25-μm cold-rolled Pd-Ag 25 wt% membranes before and after air oxidation at the same temperature as permeation. The air oxidation resulted in enhanced H₂ permeation through the membrane, as well as a roughening of the surface with the formation of surface grains and defects. The protruding grains can be leveled off by exposure to H₂ but the surface defects cannot. These microstructure changes are only on the membrane surfaces and do not create transmembrane defects that would allow permeation for gas species other than H₂. The H₂ permeability of the oxidized membrane increased by 25-90% compared to that of the as-received film at the same permeation condition, and the membranes retained perfect H₂ selectivity over N₂. The percent improvement of H₂ permeability decreases with increasing H₂ feed pressure. A new sorption kinetics hypothesis is proposed to elucidate the increase in H₂ permeability of Pd-Ag membranes caused by oxidation. H₂ solubility and sorption rate results were presented to test the new hypothesis. It is found that air oxidation does not change the H₂ solubility in Pd-Ag membranes, but enhances the H₂ sorption kinetics significantly. The extent of kinetics enhancement also decreases with increasing H₂ pressures. The much faster sorption equilibrium implies higher effective H₂ diffusivity at the Pd-Ag membrane surface for the oxidized sample and a higher transfer rate of atomic hydrogen from surface/sub-surface to the membrane bulk that contributes to the increase of H₂ permeability observed in experiments.     

Techniques for localisation of konjac glucomannan in model milk protein–polysaccharide mixed systems: Physicochemical and microscopic investigations

The effect of conjugating konjac glucomannan with fluorescein isothyocyanate (FITC) via covalent labelling on selected physicochemical properties of FITC and konjac was investigated using spectrophotometry, rheometry, and size exclusion chromatography (SEC). The binding of the lectin concanavalin A (ConA) to sugar residues of konjac was investigated using SEC. Covalent conjugation of konjac with FITC led to a shift in the absorbance spectrum peak of FITC to a lower wavelength and a decrease in the average molecular weight distribution of konjac. Furthermore, covalently labelled konjac showed reduced apparent viscosity compared to unlabelled konjac. ConA bound to the sugar residues in konjac. The potential of konjac–FITC covalent labelled conjugate or konjac–lectin labelled ConA complexes as fluorescent markers for localisation of konjac in a phase separated micellar casein–konjac mixture was investigated using confocal laser scanning microscopy. Results indicated that covalently labelled konjac has microscopic phase behaviour similar to that of un-labelled konjac and are therefore suitable for localising konjac glucomannan in a phase-separated micellar casein–konjac system.     

Effect of Transition Metals on Polysialic Acid Structure and Functions

Polysialic acid (PSA) is one of the most abundant glycopolymer present in embryonic brain, and it is known to be involved in key roles such as plasticity in the central nervous system, cell adhesion, migration and localization of neurotrophins. However, in adult brain, its expression is quite low. The exception to this is in Alzheimer′s disease (AD) brain, where significantly increased levels of polysilylated neural cell adhesion molecule (PSA‐NCAM) have been reported. Here, we confirm the role of PSA as a metal chelator, allowing it to decrease cytotoxicity caused by high levels of transition metals, commonly found in AD brain, and as a regulator of cell behavior. UV‐visible (UV‐vis) and circular dichroism (CD) spectroscopy, atomic force microscopy (AFM), and isothermal titration calorimetry (ITC) techniques were used to investigate the assembly of PSA–metals complexes. These PSA–metal complexes exhibited less toxicity compared to free metal ions, and in particular, the PSA–Cu²⁺ complex synergistically promoted neurite outgrowth in PC12 cells.     

Modeling and Evaluation of a Policy Provisioning Architecture for Mobile Ad-Hoc Networks

The ability to dynamically configure mobile ad-hoc network (MANET) devices is critical for supporting complex services such as quality of service (QoS), security and access control in these networks. In our work, we address the problem of policy distribution and provisioning in MANETs. Previously, we have proposed a policy provisioning architecture that enables the operator, e.g., a military command and control center, to maintain a logically centralized control of the network as a whole, while allowing a physically decentralized and self-managing implementation essential for a MANET environment. In this paper, we present an analytical model of the availability of the policy distribution service in a MANET and analyze the performance using stochastic Petri nets (SPNs). We develop the model at two levels of complexity: as a simple Markovian model with Poisson assumptions and as a more accurate non-Markovian model with general distributions obtained using statistical parameterization. We compare and cross-validate the analytical results with simulation and experimental results. Finally, we illustrate the effectiveness of the architecture for managing QoS for soft real-time applications, using an emulated mobile ad-hoc network testbed.