Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation

Two multinuclear complexes [Fe-6(mu(3)-O)(2)(mu(4)-O-2)L-10(OAc)(2)(H2O)(2)]center dot 2.625Et(2)O center dot 2.375H(2)O (1) and [(Fe11Cl)-Cl-III-(mu(4)-O)(3)(mu(3)-O)(5)L-16(dmf)(2.5)(H2O)(0.5)]center dot Et2O center dot 1.25dmf center dot 3.8H(2)O (2), where HL = 3,4,5-trimethoxybenzoic acid and dmf = dimethylformamide, have been prepared from trinuclear iron(III) carboxylates via their structural rearrangement in dimethylformamide or diethyl ether-dimethylformamide 9:1, respectively, and slow vapor diffusion of diethyl ether into the reaction mixture. Both compounds have been characterized by X-ray diffraction, optical, Mossbauer spectroscopy, and magnetic measurements. Complex 1 possesses a hexanuclear ferric peroxido-dioxido {Fe-6(O-2)(O)(2)}(12+) core unit, which adopts a recliner conformation, while complex 2 contains an unprecedented {Fe11O8Cl}(16+) core, in which 9 ferric ions are six-coordinate and the remaining two are five-coordinate. Another structural feature of note of the undecanuclear core is the presence of a deformed cubane entity {Fe-4(mu(3)-O)(mu(4)-O)(3)}(4+). Both complexes act as catalyst precursors for the oxidation of cyclohexane to cyclohexanol and cyclohexanone with aqueous H2O2, in the presence of pyrazinecarboxylic acid. Remarkable TONs and TOFs (the latter mainly for 1) with concomitant quite good yields have been achieved under mild conditions. Moreover, 1 exhibits remarkably high activity in an exceptionally short reaction time (45 min), being unprecedented for any metal catalyzed alkane oxidation by H2O2. The catalytic reactions proceed via Fenton type chemistry.

Monte Carlo modeling and simulations of the High Definition (HD120) micro MLC and validation against measurements for a 6 MV beam

Purpose: The most recent Varian® micro multileaf collimator(MLC), the High Definition (HD120) MLC, was modeled using the BEAMNRCMonte Carlo code. This model was incorporated into a Varian medical linear accelerator, for a 6 MV beam, in static and dynamic mode. The model was validated by comparing simulated profiles with measurements. Methods: The Varian® Trilogy® (2300C/D) accelerator model was accurately implemented using the state-of-the-art Monte Carlo simulation program BEAMNRC and validated against off-axis and depth dose profiles measured using ionization chambers, by adjusting the energy and the full width at half maximum (FWHM) of the initial electron beam. The HD120 MLC was modeled by developing a new BEAMNRC component module (CM), designated HDMLC, adapting the available DYNVMLC CM and incorporating the specific characteristics of this new micro MLC. The leaf dimensions were provided by the manufacturer. The geometry was visualized by tracing particles through the CM and recording their position when a leaf boundary is crossed. The leaf material density and abutting air gap between leaves were adjusted in order to obtain a good agreement between the simulated leakage profiles and EBT2 film measurements performed in a solid water phantom. To validate the HDMLC implementation, additional MLC static patterns were also simulated and compared to additional measurements. Furthermore, the ability to simulate dynamic MLC fields was implemented in the HDMLC CM. The simulation results of these fields were compared with EBT2 film measurements performed in a solid water phantom. Results: Overall, the discrepancies, with and without MLC, between the opened field simulations and the measurements using ionization chambers in a water phantom, for the off-axis profiles are below 2% and in depth-dose profiles are below 2% after the maximum dose depth and below 4% in the build-up region. On the conditions of these simulations, this tungsten-based MLC has a density of 18.7 g cm− 3 and an overall leakage of about 1.1 ± 0.03%. The discrepancies between the film measured and simulated closed and blocked fields are below 2% and 8%, respectively. Other measurements were performed for alternated leaf patterns and the agreement is satisfactory (to within 4%). The dynamic mode for this MLC was implemented and the discrepancies between film measurements and simulations are within 4%. Conclusions: The Varian® Trilogy® (2300 C/D) linear accelerator including the HD120 MLC was successfully modeled and simulated using the Monte CarloBEAMNRC code by developing an independent CM, the HDMLC CM, either in static and dynamic modes.

Dosimetric effect by shallow air cavities in high energy electron beams

This study evaluates the dosimetric impact caused by an air cavity located at 2 mm depth from the top surface in a PMMA phantom irradiated by electron beams produced by a Siemens Primus linear accelerator. A systematic evaluation of the effect related to the cavity area and thickness as well as to the electron beam energy was performed by using Monte Carlo simulations (EGSnrc code), Pencil Beam algorithm and Gafchromic EBT2 films. A home-PMMA phantom with the same geometry as the simulated one was specifically constructed for the measurements. Our results indicate that the presence of the cavity causes an increase (up to 70%) of the dose maximum value as well as a shift forward of the position of the depthedose curve, compared to the homogeneous one. Pronounced dose discontinuities in the regions close to the lateral cavity edges are observed. The shape and magnitude of these discontinuities change with the dimension of the cavity. It is also found that the cavity effect is more pronounced (6%) for the 12 MeV electron beam and the presence of cavities with large thickness and small area introduces more significant variations (up to 70%) on the depthedose curves. Overall, the Gafchromic EBT2 film measurements were found in agreement within 3% with Monte Carlo calculations and predict well the fine details of the dosimetric change near the cavity interface. The Pencil Beam calculations underestimate the dose up to 40% compared to Monte Carlo simulations; in particular for the largest cavity thickness (2.8 cm).

Adaptive mutations in bacteria: high rate and small effects

Evolution by natural selection is driven by the continuous generation of adaptive mutations. We measured the genomic mutation rate that generates beneficial mutations and their effects on fitness in Escherichia coli under conditions in which the effect of competition between lineages carrying different beneficial mutations is minimized. We found a rate on the order of 10–5 per genome per generation, which is 1000 times as high as previous estimates, and a mean selective advantage of 1%. Such a high rate of adaptive evolution has implications for the evolution of antibiotic resistance and pathogenicity.

High Performance Multi-Standard Architecture for DCT Computation in H.264/AVC High Profile and HEVC Codecs

A new high performance architecture for the computation of all the DCT operations adopted in the H.264/AVC and HEVC standards is proposed in this paper. Contrasting to other dedicated transform cores, the presented multi-standard transform architecture is supported on a completely configurable, scalable and unified structure, that is able to compute not only the forward and the inverse 8×8 and 4×4 integer DCTs and the 4×4 and 2×2 Hadamard transforms defined in the H.264/AVC standard, but also the 4×4, 8×8, 16×16 and 32×32 integer transforms adopted in HEVC. Experimental results obtained using a Xilinx Virtex-7 FPGA demonstrated the superior performance and hardware efficiency levels provided by the proposed structure, which outperforms its more prominent related designs by at least 1.8 times. When integrated in a multi-core embedded system, this architecture allows the computation, in real-time, of all the transforms mentioned above for resolutions as high as the 8k Ultra High Definition Television (UHDTV) (7680×4320 @ 30fps).

Electrodeposition and characterization of nickel–copper metallic foams for application as electrodes for supercapacitors

Nickel-copper metallic foams were electrodeposited from an acidic electrolyte, using hydrogen bubble evolution as a dynamic template. Their morphology and chemical composition was studied by scanning electron microscopy and related to the deposition parameters (applied current density and deposition time). For high currents densities (above 1 A cm(-2)) the nickel-copper deposits have a three-dimensional foam-like morphology with randomly distributed nearly-circular pores whose walls present an open dendritic structure. The nickel-copper foams are crystalline and composed of pure nickel and a copper-rich phase containing nickel in solid solution. The electrochemical behaviour of the material was studied by cyclic voltammetry and chronopotentiometry (charge-discharge curves) aiming at its application as a positive electrode for supercapacitors. Cyclic voltammograms showed that the Ni-Cu foams have a pseudocapacitive behaviour. The specific capacitance was calculated from charge-discharge data and the best value (105 F g(-1) at 1 mA cm(-2)) was obtained for nickel-copper foams deposited at 1.8 A cm(-2) for 180 s. Cycling stability of these foams was also assessed and they present a 90 % capacitance retention after 10,000 cycles at 10 mA cm(-2).

Efeito dos parâmetros técnicos na dose e qualidade de imagem num sistema de radiografia computorizada

Mestrado em Radiações Aplicadas às Tecnologias da Saúde - Ramo de especialização: Imagem Digital com Radiação X

Climatology of the Iberia coastal low-level wind jet: weather research forecasting model high-resolution results

Coastal low-level jets (CLLJ) are a low-tropospheric wind feature driven by the pressure gradient produced by a sharp contrast between high temperatures over land and lower temperatures over the sea. This contrast between the cold ocean and the warm land in the summer is intensified by the impact of the coastal parallel winds on the ocean generating upwelling currents, sharpening the temperature gradient close to the coast and giving rise to strong baroclinic structures at the coast. During summertime, the Iberian Peninsula is often under the effect of the Azores High and of a thermal low pressure system inland, leading to a seasonal wind, in the west coast, called the Nortada (northerly wind). This study presents a regional climatology of the CLLJ off the west coast of the Iberian Peninsula, based on a 9km resolution downscaling dataset, produced using the Weather Research and Forecasting (WRF) mesoscale model, forced by 19 years of ERA-Interim reanalysis (1989-2007). The simulation results show that the jet hourly frequency of occurrence in the summer is above 30% and decreases to about 10% during spring and autumn. The monthly frequencies of occurrence can reach higher values, around 40% in summer months, and reveal large inter-annual variability in all three seasons. In the summer, at a daily base, the CLLJ is present in almost 70% of the days. The CLLJ wind direction is mostly from north-northeasterly and occurs more persistently in three areas where the interaction of the jet flow with local capes and headlands is more pronounced. The coastal jets in this area occur at heights between 300 and 400 m, and its speed has a mean around 15 m/s, reaching maximum speeds of 25 m/s.

A VLF to UHF propagation model for evaluation of high-speed railway electromagnetic interference in RF monitoring base-stations

Considering that recent european high-speed railway system has a traction power system of kV 50 Hz, which causes electromagnetic emission for the outside world, it is important to dimension the railway system emissions, using a frequency/distance dependent propagation model. This paper presents an enhanced theoretical model for VLF to UHF propagation, railway system oriented. It introduces the near field approach (crucial in low frequency propagation) and also considers the source characteristics and type of measuring antenna. Simulations are presented, and comparisons are set with earlier far field models. Using the developed model, a real case study was performed in partnership with Refer Telecom (portuguese telecom operator for railways). The new propagation model was used in order to predict the future high-speed railway electromagnetic emissions in the Lisbon north track. The results show the model's prediction capabilities and also its applicability to realistic scenarios.

Trends Of CPU, GPU and FPGA for high-performance computing

Floating-point computing with more than one TFLOP of peak performance is already a reality in recent Field-Programmable Gate Arrays (FPGA). General-Purpose Graphics Processing Units (GPGPU) and recent many-core CPUs have also taken advantage of the recent technological innovations in integrated circuit (IC) design and had also dramatically improved their peak performances. In this paper, we compare the trends of these computing architectures for high-performance computing and survey these platforms in the execution of algorithms belonging to different scientific application domains. Trends in peak performance, power consumption and sustained performances, for particular applications, show that FPGAs are increasing the gap to GPUs and many-core CPUs moving them away from high-performance computing with intensive floating-point calculations. FPGAs become competitive for custom floating-point or fixed-point representations, for smaller input sizes of certain algorithms, for combinational logic problems and parallel map-reduce problems. © 2014 Technical University of Munich (TUM).

Unified transform architecture for AVC, AVS, VC-1 and HEVC high-performance codecs

A unified architecture for fast and efficient computation of the set of two-dimensional (2-D) transforms adopted by the most recent state-of-the-art digital video standards is presented in this paper. Contrasting to other designs with similar functionality, the presented architecture is supported on a scalable, modular and completely configurable processing structure. This flexible structure not only allows to easily reconfigure the architecture to support different transform kernels, but it also permits its resizing to efficiently support transforms of different orders (e. g. order-4, order-8, order-16 and order-32). Consequently, not only is it highly suitable to realize high-performance multi-standard transform cores, but it also offers highly efficient implementations of specialized processing structures addressing only a reduced subset of transforms that are used by a specific video standard. The experimental results that were obtained by prototyping several configurations of this processing structure in a Xilinx Virtex-7 FPGA show the superior performance and hardware efficiency levels provided by the proposed unified architecture for the implementation of transform cores for the Advanced Video Coding (AVC), Audio Video coding Standard (AVS), VC-1 and High Efficiency Video Coding (HEVC) standards. In addition, such results also demonstrate the ability of this processing structure to realize multi-standard transform cores supporting all the standards mentioned above and that are capable of processing the 8k Ultra High Definition Television (UHDTV) video format (7,680 x 4,320 at 30 fps) in real time.

Modular high-current generator for electromagnetic forming with energy recovery

A 10 kJ electromagnetic forming (EMF) modulator with energy recovery based on two resonant power modules, each containing a 4.5 kV/30-kA silicon controlled rectifier, a 1.11-mF capacitor bank and an energy recovery circuit, working in parallel to allow a maximum actuator discharge current amplitude and rate of 50 kA and 2 kA/mu s was successfully developed and tested. It can be plugged in standard single phase 230 V/16 A mains socket and the circuit is able to recover up to 32% of its initial energy, reducing the charging time of conventional EMF systems by up to 68%.

Multilevel high-voltage pulse generation based on a new modular solid-state switch

This paper describes a modular solid-state switching cell derived from the Marx generator concept to be used in topologies for generating multilevel unipolar and bipolar high-voltage (HV) pulses into resistive loads. The switching modular cell comprises two ON/OFF semiconductors, a diode, and a capacitor. This cell can be stacked, being the capacitors charged in series and their voltages balanced in parallel. To balance each capacitor voltage without needing any parameter measurement, a vector decision diode algorithm is used in each cell to drive the two switches. Simulation and experimental results, for generating multilevel unipolar and bipolar HV pulses into resistive loads are presented.

Copper-organic frameworks assembled from in situ generated 5-(4-pyridyl) tetrazole building blocks: synthesis, structural features, topological analysis and catalytic oxidation of alcohols

Two new metal- organic compounds {[Cu-3(mu(3)-4-(p)tz)(4)(mu(2)-N-3)(2)(DMF)(2)](DMF)(2)}(n) (1) and {[Cu(4ptz) (2)(H2O)(2)]}(n) (2) {4-ptz = 5-(4-pyridyl)tetrazolate} with 3D and 2D coordination networks, respectively, have been synthesized while studying the effect of reaction conditions on the coordination modes of 4-pytz by employing the [2 + 3] cycloaddition as a tool for generating in situ the 5-substituted tetrazole ligands from 4-pyridinecarbonitrile and NaN3 in the presence of a copper(II) salt. The obtained compounds have been structurally characterized and the topological analysis of 1 discloses a topologically unique trinodal 3,5,6-connected 3D network which, upon further simplification, results in a uninodal 8-connected underlying net with the bcu (body centred cubic) topology driven by the [Cu-3(mu(2)-N-3)(2)] cluster nodes and mu(3)-4-ptz linkers. In contrast, the 2D metal-organic network in 2 has been classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology assembled from the Cu nodes and mu(2)-4-ptz linkers. The catalytic investigations disclosed that 1 and 2 act as active catalyst precursors towards the microwave-assisted homogeneous oxidation of secondary alcohols (1-phenylethanol, cyclohexanol, 2-hexanol, 3-hexanol, 2-octanol and 3-octanol) with tert-butylhydroperoxide, leading to the yields of the corresponding ketones up to 86% (TOF = 430 h(-1)) and 58% (TOF = 290 h(-1)) in the oxidation of 1-phenylethanol and cyclohexanol, respectively, after 1 h under low power ( 10 W) microwave irradiation, and in the absence of any added solvent or additive.

Microwave-assisted and solvent-free peroxidative oxidation of 1-phenylethanol to acetophenone with a CuII-TEMPO catalytic system

The water-soluble copper(II) complex [Cu(H2R)(HL)]center dot H2O (1) was prepared by reaction of copper(II) nitrate hydrate with (E)-2-(((1-hydroxynaphthalen-2-yl)methylene)amino) benzenesulfonic acid (H2L) and diethanolamine (H3R). It was characterized by IR and ESI-MS spectroscopies, elemental and X-ray crystal structural analyses. 1 shows a high catalytic activity for the solvent-free microwave (MW) assisted oxidation of 1-phenylethanol with tert-butylhydroperoxide, leading, in the presence of TEMPO, to yields up to 85% (TON = 850) in a remarkably short reaction time (15 min, with the corresponding TOE value of 3.40 x 10(3) h(-1)) under low power (25W) MW irradiation. Crown Copyright (C) 2014 Published by Elsevier B.V. All rights reserved.