Detailed analysis of the charge transfer complex N,N-dimethylaniline-SO(2) by Raman spectroscopy and density functional theory calculations

Although the amine sulfur dioxide chemistry was well characterized in the past both experimentally and theoretically, no systematic Raman spectroscopic study describes the interaction between N,N-dimethylaniline (DMA) and sulfur dioxide (SO(2)). The formation of a deep red oil by the reaction of SO(2) with DMA is an evidence of the charge transfer (CT) nature of the DMA-SO(2) interaction. The DMA -SO(2) normal Raman spectrum shows the appearance of two intense bands at 1110 and 1151 cm(-1), which are enhanced when resonance is approached. These bands are assigned to nu(s)(SO(2)) and nu(phi-N) vibrational modes, respectively, confirming the interaction between SO(2) and the amine via the nitrogen atom. The dimethyl group steric effect favors the interaction of SO(2) with the ring pi electrons, which gives rise to a pi-pi* low-energy CT electronic transition, as confirmed by time-dependent density functional theory (TDDFT) calculations. In addition, the calculated Raman DMA-SO(2) spectrum at the B3LYP/6-311++g(3df,3pd) level shows good agreement with the experimental results (vibrational wavenumbers and relative intensities), allowing a complete assignment of the vibrational modes. A better understanding of the intermolecular interactions in this model system can be extremely useful in designing new materials to absorb, detect, or even quantify SO(2). Copyright (C) 2009 John Wiley & Sons, Ltd.

Photocatalytic degradation of methylene blue by TiO(2)-Cu thin films: Theoretical and experimental study

In this work the effect of doping concentration and depth profile of Cu atoms on the photocatalytic and surface properties of TiO(2) films were studied. TiO(2) films of about 200 nn thickness were deposited on glass substrates on which a thin Cu layer (5 nm) was deposited. The films were annealed during 1 s to 100 degrees C and 400 degrees C, followed by chemical etching of the Cu film. The grazing incidence X-ray fluorescence measurements showed a thermal induced migration of Cu atoms to depths between 7 and 31 nm. The X-ray photoelectron spectroscopy analysis detected the presence of TiO(2), Cu(2)O and Cu(0) phases and an increasing Cu content with the annealing temperature. The change of the surface properties was monitored by the increasing red-shift and absorption of the ultraviolet-visible spectra. Contact angle measurements revealed the formation of a highly hydrophilic surface for the film having a medium Cu concentration. For this sample photocatalytic assays, performed by methylene blue discoloration, show the highest activity. The proposed mechanism of the catalytic effect, taking place on Ti/Cu sites, is supported by results obtained by theoretical calculations. (C) 2010 Elsevier B.V. All rights reserved.

The interaction between atoms of Au and Cu with clean Si(111) surface: A study combining synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations

In order to evaluate the interactions between Au/Cu atoms and clean Si(l 11) surface, we used synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations. Optimized geometries and energies on different adsorption sites indicate that the binding energies at different adsorption sites are high, suggesting a strong interaction between metal atom and silicon surface. The Au atom showed higher interaction than Cu atom. The theoretical and experimental data showed good agreement. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

Structural studies of prephenate dehydratase from Mycobacterium tuberculosis H37Rv by SAXS, ultracentrifugation, and computational analysis

Tuberculosis (TB) is one of the most common infectious diseases known to man and responsible for millions of human deaths in the world. The increasing incidence of TB in developing countries, the proliferation of multidrug resistant strains, and the absence of resources for treatment have highlighted the need of developing new drugs against TB. The shikimate pathway leads to the biosynthesis of chorismate, a precursor of aromatic amino acids. This pathway is absent from mammals and shown to be essential for the survival of Mycobacterium tuberculosis, the causative agent of TB. Accordingly, enzymes of aromatic amino acid biosynthesis pathway represent promising targets for structure-based drug design. The first reaction in phenylalanine biosynthesis involves the conversion of chorismate to prephenate, catalyzed by chorismate mutase. The second reaction is catalyzed by prephenate dehydratase (PDT) and involves decarboxylation and dehydratation of prephenate to form phenylpyruvate, the precursor of phenylalanine. Here, we describe utilization of different techniques to infer the structure of M. tuberculosis PDT (MtbPDT) in solution. Small angle X-ray scattering and ultracentrifugation analysis showed that the protein oligomeric state is a tetramer and MtbPDT is a flat disk protein. Bioinformatics tools were used to infer the structure of MtbPDT A molecular model for MtbPDT is presented and molecular dynamics simulations indicate that MtbPDT i.s stable. Experimental and molecular modeling results were in agreement and provide evidence for a tetrameric state of MtbPDT in solution.

Synthesis, characterization and biological analysis of the complex [VO(Hdhp)(2)] (H(2)dhp=2,3-dihydroxypyridine)

A new vanadium (IV) complex with the monoanion of 2,3-dihydroxypyridine (H(2)dhp), or 3-hydroxy-2(1H)-pyridone, was synthesized, characterized by physicochemical techniques and tested biologically. The EPR data for the [VO(Hdhp)(2)] complex in DMF are: g(x) = 1.9768, g(y) = 1.9768 and g(z) = 1.9390; A values (10(-4) cm(-1)): A(x), 59.4; A(y//), 59.4; A(z), 171.0. The vV=O band in the IR spectrum of the complex is at 986 cm(-1). The complex is paramagnetic, with mu(eff) = 1.65 BM (d(1), spin-only) at 25 degrees C. The irreversible oxidation process [V(V)/V(IV)] of the [VO(Hdhp)(2)] complex, as revealed in a cyclic voltammogram, occurs at 876 mV. The calculated molecular structure of [VO(Hdhp)(2)] shows the vanadium(IV) center in a distorted square pyramidal environment, with the oxo ligand in the apical position and the oxygen donor atoms of the Hdhp ligands in the basal positions. The ability of [VO(Hdhp)(2)] to mimic insulin, and its toxicity to hepato-biliary functions, were investigated in streptozotocin-induced diabetic rats and it was concluded that the length of treatment and the amount of [VO(Hdhp)(2)] administered were effective in reducing experimental diabetes.

Experimental and computational investigation of the roll forming process

One of the first questions to consider when designing a new roll forming line is the number of forming steps required to produce a profile. The number depends on material properties, the cross-section geometry and tolerance requirements, but the tool designer also wants to minimize the number of forming steps in order to reduce the investment costs for the customer. There are several computer aided engineering systems on the market that can assist the tool designing process. These include more or less simple formulas to predict deformation during forming as well as the number of forming steps. In recent years it has also become possible to use finite element analysis for the design of roll forming processes. The objective of the work presented in this thesis was to answer the following question: How should the roll forming process be designed for complex geometries and/or high strength steels? The work approach included both literature studies as well as experimental and modelling work. The experimental part gave direct insight into the process and was also used to develop and validate models of the process. Starting with simple geometries and standard steels the work progressed to more complex profiles of variable depth and width, made of high strength steels. The results obtained are published in seven papers appended to this thesis. In the first study (see paper 1) a finite element model for investigating the roll forming of a U-profile was built. It was used to investigate the effect on longitudinal peak membrane strain and deformation length when yield strength increases, see paper 2 and 3. The simulations showed that the peak strain decreases whereas the deformation length increases when the yield strength increases. The studies described in paper 4 and 5 measured roll load, roll torque, springback and strain history during the U-profile forming process. The measurement results were used to validate the finite element model in paper 1. The results presented in paper 6 shows that the formability of stainless steel (e.g. AISI 301), that in the cold rolled condition has a large martensite fraction, can be substantially increased by heating the bending zone. The heated area will then become austenitic and ductile before the roll forming. Thanks to the phenomenon of strain induced martensite formation, the steel will regain the martensite content and its strength during the subsequent plastic straining. Finally, a new tooling concept for profiles with variable cross-sections is presented in paper 7. The overall conclusions of the present work are that today, it is possible to successfully develop profiles of complex geometries (3D roll forming) in high strength steels and that finite element simulation can be a useful tool in the design of the roll forming process.

Modelling dominance in a flexible intercross analysis

The aim of this paper is to develop a flexible model for analysis of quantitative trait loci (QTL) in outbred line crosses, which includes both additive and dominance effects. Our flexible intercross analysis (FIA) model accounts for QTL that are not fixed within founder lines and is based on the variance component framework. Genome scans with FIA are performed using a score statistic, which does not require variance component estimation. RESULTS: Simulations of a pedigree with 800 F2 individuals showed that the power of FIA including both additive and dominance effects was almost 50% for a QTL with equal allele frequencies in both lines with complete dominance and a moderate effect, whereas the power of a traditional regression model was equal to the chosen significance value of 5%. The power of FIA without dominance effects included in the model was close to those obtained for FIA with dominance for all simulated cases except for QTL with overdominant effects. A genome-wide linkage analysis of experimental data from an F2 intercross between Red Jungle Fowl and White Leghorn was performed with both additive and dominance effects included in FIA. The score values for chicken body weight at 200 days of age were similar to those obtained in FIA analysis without dominance. CONCLUSION: We have extended FIA to include QTL dominance effects. The power of FIA was superior, or similar, to standard regression methods for QTL effects with dominance. The difference in power for FIA with or without dominance is expected to be small as long as the QTL effects are not overdominant. We suggest that FIA with only additive effects should be the standard model to be used, especially since it is more computationally efficient.

Reliability of GPS based traffic data: an experimental evaluation

GPS tracking of mobile objects provides spatial and temporal data for a broad range of applications including traffic management and control, transportation routing and planning. Previous transport research has focused on GPS tracking data as an appealing alternative to travel diaries. Moreover, the GPS based data are gradually becoming a cornerstone for real-time traffic management. Tracking data of vehicles from GPS devices are however susceptible to measurement errors – a neglected issue in transport research. By conducting a randomized experiment, we assess the reliability of GPS based traffic data on geographical position, velocity, and altitude for three types of vehicles; bike, car, and bus. We find the geographical positioning reliable, but with an error greater than postulated by the manufacturer and a non-negligible risk for aberrant positioning. Velocity is slightly underestimated, whereas altitude measurements are unreliable.

An Experimental Study of Submerged Entry Nozzles (SEN) Focusing on Decarburization and Clogging

The submerged entry nozzle (SEN) is used to transport the molten steel from a tundish to a mould. The main purpose of its usage is to prevent oxygen and nitrogen pick-up by molten steel from the gas. Furthermore, to achieve the desired flow conditions in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. In addition, the steelmaking processes occur at high temperatures around 1873 K, so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during preheating and casting processes is necessary for the design of the steelmaking processes  The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during preheating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied. A large number of accretion samples formed inside alumina-graphite clogged SENs were examined using FEG-SEM-EDS and Feature analysis. The internal coated SENs were used for continuous casting of stainless steel grades alloyed with Rare Earth Metals (REM). The post-mortem study results clearly revealed the formation of a multi-layer accretion. A harmful effect of the SENs decarburization on the accretion thickness was also indicated. In addition, the results indicated a penetration of the formed alkaline-rich glaze into the alumina-graphite base refractory. More specifically, the alkaline-rich glaze reacts with graphite to form a carbon monoxide gas. Thereafter, dissociation of CO at the interface between SEN and molten metal takes place. This leads to reoxidation of dissolved alloying elements such as REM (Rare Earth Metal). This reoxidation forms the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, the interaction of the penetrated glaze with alumina in the SEN base refractory materials leads to the formation of a high-viscous alumina-rich glaze during the SEN preheating process. This, in turn, creates a very uneven surface at the SEN internal surface. Furthermore, these uneven areas react with dissolved REM in molten steel to form REM aluminates, REM silicates and REM alumina-silicates. The formation of the large “in-situ” REM oxides and the reaction of the REM alloying elements with the previously mentioned SEN´s uneven areas may provide a large REM-rich surface in contact with the primary inclusions in molten steel. This may facilitate the attraction and agglomeration of the primary REM oxide inclusions on the SEN internal surface and thereafter the clogging. The study revealed the disadvantages of the glass/silicon powder coating applications and the SEN decarburization. The decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials from a commercial Submerged Entry Nozzle (SEN), were also investigated for different gas atmospheres consisting of CO2, O2 and Ar. The gas ratio values were kept the same as it is in a propane combustion flue gas at different Air-Fuel-Ratio (AFR) values for both Air-Fuel and Oxygen-Fuel combustion systems. Laboratory experiments were carried out under nonisothermal conditions followed by isothermal heating. The decarburization ratio (α) values of all three refractory types were determined by measuring the real time weight losses of the samples. The results showed the higher decarburization ratio (α) values increasing for MgO-C refractory when changing the Air-Fuel combustion to Oxygen-Fuel combustion at the same AFR value. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times compared to heating at lower temperatures during longer holding times for Al2O3-C samples. Diffusion models were proposed for estimation of the decarburization rate of an Al2O3-C refractory in the SEN. Two different methods were studied to prevent the SEN decarburization during preheating: The effect of an ZrSi2 antioxidant and the coexistence of an antioxidant additive and a (4B2O3 ·BaO) glass powder on carbon oxidation for non-isothermal and isothermal heating conditions in a controlled atmosphere. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 ·BaO) glass powder of the total alumina-graphite refractory base materials, presented the most effective resistance to carbon oxidation. The 121% volume expansion due to the Zircon formation during heating and filling up the open pores by a (4B2O3 ·BaO) glaze during the green body sintering led to an excellent carbon oxidation resistance. The effects of the plasma spray-PVD coating of the Yttria Stabilized Zirconia (YSZ) powder on the carbon oxidation of the Al2O3-C coated samples were investigated. Trials were performed at non-isothermal heating conditions in a controlled atmosphere. Also, the applied temperature profile for the laboratory trials were defined based on the industrial preheating trials. The controlled atmospheres consisted of CO2, O2 and Ar. The thicknesses of the decarburized layers were measured and examined using light optic microscopy, FEG-SEM and EDS. A 250-290 μm YSZ coating is suggested to be an appropriate coating, as it provides both an even surface as well as prevention of the decarburization even during heating in air. In addition, the interactions between the YSZ coated alumina-graphite refractory base materials in contact with a cerium alloyed molten stainless steel were surveyed. The YSZ coating provided a total prevention of the alumina reduction by cerium. Therefore, the prevention of the first clogging product formed on the surface of the SEN refractory base materials. Therefore, the YSZ plasma-PVD coating can be recommended for coating of the hot surface of the commercial SENs.

Design and validation of a sheet metal shearing experimental procedure

Throughout the industrial processes of sheet metal manufacturing and refining, shear cutting is widely used for its speed and cost advantages over competing cutting methods. Industrial shears may include some force measurement possibilities, but the force is most likely influenced by friction losses between shear tool and the point of measurement, and are in general not showing the actual force applied to the sheet. Well defined shears and accurate measurements of force and shear tool position are important for understanding the influence of shear parameters. Accurate experimental data are also necessary for calibration of numerical shear models. Here, a dedicated laboratory set-up with well defined geometry and movement in the shear, and high measurability in terms of force and geometry is designed, built and verified. Parameters important to the shear process are studied with perturbation analysis techniques and requirements on input parameter accuracy are formulated to meet experimental output demands. Input parameters in shearing are mostly geometric parameters, but also material properties and contact conditions. Based on the accuracy requirements, a symmetric experiment with internal balancing of forces is constructed to avoid guides and corresponding friction losses. Finally, the experimental procedure is validated through shearing of a medium grade steel. With the obtained experimental set-up performance, force changes as result of changes in studied input parameters are distinguishable down to a level of 1%.

Theoretical and experimental optical holography

The intent of this paper is to present an analysis of optical holography. Both the physical theory behind holography and the experimental techniques used in making holograms will be presented. To accomplish this goal, the paper is divided into two independent sections: the theoretical section followed by the experimental section. Each section is intended to be a complete unit. The Theoretical Section is an exposure to the theory behind holography. This consists of a review of the concepts of interference and diffraction. followed by a brief review of partial coherence. The remaining part of the Theoretical Section is devoted to the mathematical analysis of optical holography. The Experimental Section begins with an introduction to the equipment and facilities currently available for optical holography at Colby College. Holographic procedures is dominated by the description of transmission holography (v.s. reflection. or white-light. holography). After these general holographic procedures a few variations on the basic transmission hologram are presented. The experimental section will end with an introduction to holographic interferometry, a major application of holographic techniques.