Tetrapyrazinoporphyrazines with different number of peripheral pyridyl rings: Synthesis,photophysical and photochemical properties

Zinc tetrapyrazinoporphyrazines comprising different numbers of pyridin-2-yl and tert-butylsulfanyl substituents were prepared by the statistical condensation of two precursors – 5,6-bis(tert-butylsulfanyl)pyrazine-2,3-dicarbonitrile (A) and 5,6-dipyridin-2-yl-pyrazine-2,3-dicarbonitrile (B). The ensuing zinc tetrapyrazinoporphyrazines were chromatographically separated on silica column and characterized. Adjacent (AABB) and opposite (ABAB) isomers were not separated. The prepared zinc tetrapyrazinoporphyrazines did not differ in their Q-band position but the B-band position was shifted hypsochromically for compounds bearing more pyridyl units; in addition, a weak band at 450–520 nm decreased with increasing number of pyridyl substituents. Singlet oxygen quantum yields (Φ_Δ in the range 0.69–0.53) decreased with increasing number of pyridyl units on the macrocyclic core, while fluorescence quantum yields showed the reverse tendency (Φ_F in the range 0.22–0.26).     

Preliminary investigation of factors determining self-organised structures preparation in polymer layers

Factors determining creation of self-organized structures, Bénar–Marangoni cells, during the process of solvent evaporation from the polymer solution and formation of polymer film were studied. Examined parameters were temperature, temperature gradient, rate of drying, height of a liquid layer, area for film preparation, viscosity, molecular weight distribution, etc. A special apparatus, micro condensation drying system, was engineered for this study. As a model system, hydroxyethyl cellulose aqueous solution was used for its excellent film-forming ability and the tendency to self-aggregation. Experimental results, presented in a wide spectrum of self-organized patterns, show the complexity of the problem and the crucial role of molecular weight distribution of the polymer in the fixation of organized structures under highly non-equilibrium conditions.     

A posteriori optimization of parameters in stabilized methods for convection–diffusion problems – Part I

Stabilized finite element methods for convection-dominated problems require the choice of appropriate stabilization parameters. From numerical analysis, often only their asymptotic values are known. This paper presents a general framework for optimizing stabilization parameters with respect to the minimization of a target functional. Exemplarily, this framework is applied to the SUPG finite element method and the minimization of a residual-based error estimator, an error indicator, and a functional including the crosswind derivative of the computed solution. Benefits of the basic approach are demonstrated by means of numerical results.     

The Rengen Grassland Experiment: soil contamination by trace elements after 65 years of Ca,N, P and K fertiliser application

The Rengen Grassland Experiment (RGE) was established in the Eifel Mts. (Germany) on a low productive Nardetum in 1941. Since then, the following fertiliser treatments have been applied along with a two cut system: unfertilised control, Ca, CaN, CaNP, CaNP–KCl and CaNP–K₂SO₄ with basic slag (syn. Thomas phosphate) as the only P fertiliser. The effect of long-term fertilisation on plant-available (extracted with 0.01 mol l⁻¹ CaCl₂), easily-mobilisable (extracted with 0.05 mol l⁻¹ EDTA), potentially-mobilisable (extracted with 2 mol l⁻¹ HNO₃) and total concentrations of trace elements (As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) in the top 0–10 and 10–20 cm of soil were investigated in 2006. According to redundancy analysis (RDA), the effect of treatment on the concentrations of risk elements was significant and explained 82.3 and 90.6% of the variability in the data in the 0–10 and 10–20 cm soil layers, respectively. Basic slag supplied the soil with considerable amounts of As, Cr, Cu, Fe, Mn and Zn. Following 65 years of fertiliser application the concentrations of risk elements in the soil profile had increased substantially, especially with basic slag. However, threshold limits for total trace element concentration in soil permitted by Czech national legislation were exceeded only in the case of As. The increase in plant-available As concentrations was most critical as it increased the potential uptake of As by plants in plots fertilised with P. Although P treatments received more than 300 g of Cr ha⁻¹ annually, no effect on plant-available Cr soil content was detected. This contrasted with the accumulation of total Cr in the 0–10 and 10–20 cm soil layers. Furthermore, plant availability of Cd, Fe, Mn and Zn was affected by soil pH and generally decreased with the application of quick lime. Plant availability of these elements was not correlated with amounts supplied by fertilisers.     

Morphological co-processing unit for embedded devices

This paper focuses on the development of a fully programmable morphological coprocessor for embedded devices. It is a well-known fact that the majority of morphological processing operations are composed of a (potentially large) number of sequential elementary operators. At the same time, the industrial context induces a high demand on robustness and decision liability that makes the application even more demanding. Recent stationary platforms (PC, GPU, clusters) no more represent a computational bottleneck in real-time vision or image processing applications. However, in embedded solutions such applications still hit computational limits. The morphological co-processing unit (MCPU) replies to this demand. It assembles the previously published efficient dilation/erosion units with geodesic units and ALUs to support a larger collection of morphological operations, from a simple dilation to serial filters involving a geodesic reconstruction step. The coprocessor has been integrated into an FPGA platform running a server that is able to respond to client’s requests over the ethernet. The experimental performance of the MCPU measured on a wide set of operations brings as results in orders of magnitude better than another embedded platform, built around an ARM A9 quad-core processor.     

Off-axis and inline electron holography: Experimental comparison

Electron holography is a very powerful technique for mapping static electric and magnetic potentials down to atomic resolution. While electron holography is commonly considered synonymous with its off-axis variant in the high energy electron microscopy community, inline electron holography is widely applied in low-energy electron microscopy, where the realization of the off-axis setup is still an experimental challenge. This paper demonstrates that both inline and off-axis holography may be used to recover amplitude and phase shift of the very same object, in our example latex spheres of 90 and 200 nm in diameter, producing very similar results, provided the object does not charge under the electron beam.     

The effect of temperature on the pulsed current processing behaviour and structural characteristics of porous ZSM-5 and zeolite Y monoliths

Hierachically porous monoliths of ZSM-5 and Y zeolites have been prepared by pulsed current processing (PCP). The densification behaviour and structural characteristics during rapid thermal treatment of the zeolites have been determined and related to the influence of the Si:Al ratio on the thermal stability of the zeolites. Monoliths of macroscopic shape can be prepared with an insignificant loss of surface area and micropore volume when the PCP-treatment was performed at temperatures below a critical maximum PCP temperature (T_PCP). Full-profile fittings of the powder X-ray diffraction patterns showed that the lattice strain of zeolite Y increases rapidly above the critical T_PCP while the ZSM-5 zeolites undergo a phase transition from orthorhombic to monoclinic. The use of a novel ceramic processing route for the production of the zeolite monoliths that do not significantly influence the structural characteristics and surface area of the starting materials has a potential to be of importance in catalysis and gas separation applications.     

Thermal oxidation of CVD diamond

A thermal oxidation process of diamond films grown by chemical vapor deposition (CVD) has been studied. The oxidation was realized via heating of the CVD films in air. Pristine and oxidized CVD diamond films were analyzed with Raman spectroscopy and scanning electron microscopy (SEM) techniques. Raman spectroscopy revealed substantial changes in the polycrystalline diamond film composition induced by oxidation. A selective oxidation of disordered carbon and small size diamond crystallites was obtained at appropriate temperatures. A model explaining the formation and oxidation of the CVD diamond films containing the micrometer single diamond cores surrounded by the nanocrystalline diamond and disordered carbon has been proposed on the basis of the obtained results.     

Optical characterization of ultrananocrystalline diamond films

Optical properties of the ultrananocrystalline diamond films were studied by multi-sample method based on the combination of variable angle spectroscopic ellipsometry and spectroscopic reflectometry applied in the range 0.6–6.5 eV. The films were deposited by PECVD in a conventional bell jar (ASTeX type) reactor using dual frequency discharge, microwave cavity plasma and radio frequency plasma inducing dc self-bias at a substrate holder. The optical model of the samples included a surface roughness described by the Rayleigh–Rice theory and a refractive index profile in which Drude approximation was used. The results conformed with the present understanding of the polycrystalline diamond growth on the silicon substrate because the existence of silicon carbide and amorphous hydrogenated carbon film between the silicon substrate and nucleation layer was proved.     

Priority discarding of speech in integrated packet networks

The authors discuss the control of short-term congestion, which is referred to as overload, in integrated packet networks (IPNs) containing a mix of data, speech, and possibly other types of signals. A system model is proposed that assigns a delivery priority to each packet (speech or otherwise) at the transmitter and discards speech packets according to delivery priority at any point in the network in response to overload. This model attempts to minimize per-packet processing at networks nodes. The research described is guided by two principles for IPN design: minimal per-packet processing and flexibility due to signal structure. The quality of the received speech is maintained by classifying speech segments according to their structure and coding them in a way that ensures ease of lost-packet regeneration at the receiver. The results of an experiment are reported that confirmed the general validity of this model from the standpoint of transmitter and receiver processing and subjective quality