Spectrophotometric Determination of Captopril Through Charge Transfer Complex Formation Using Fractional Factorial and Central Composite Design

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Simple and fast spectrophotometric determination of H2O2 in photo-Fenton reactions using metavanadate

This work proposes a spectrophotometric method for the determination of hydrogen peroxide during photodegradation reactions. The method is based on the reaction of H2O2 with amonium metavanadate in acidic medium, which results in the formation of a red-orange color peroxovanadium cation, with maximum absorbance at 450 nm. The method was optimized using the multivariate analysis providing the minimum concentration of vanadate (6.2 mmol L-1) for the maximum absorbance signal. Under these conditions, the detection limit is 143 mu mol L-1. The reaction product showed to be very stable for samples of peroxide concentrations up to 3 mmol L-1 at room temperature during 180 h. For higher concentrations however, samples must be kept refrigerated (4 degrees C) or diluted. The method showed no interference of Cl- (0.2-1.3 mmol L-1), NO3- (0.3-1.0 mmol L-1), Fe3+, (0.2-1.2 mmol L-1) and 2,4-dichlorophenol (DCP) (0.2-1.0 mmol L-1). When compared to iodometric titration, the vanadate method showed a good agreament. The method was applied for the evaluation of peroxide consumption during photo-Fenton degradation of 2,4-dichlorophenol using blacklight irradiation. (c) 2004 Elsevier B.V. All rights reserved.

Simultaneous spectrometric determination of Cu2+, Mn2+ and Zn2+ in polivitaminic/polimineral drug using SPA and GA algorithms for variable selection

Este artigo apresenta uma aplicação do método para determinação espectrofotométrica simultânea dos íons divalentes de cobre, manganês e zinco à análise de medicamento polivitamínico/polimineral. O método usa 4-(2-piridilazo) resorcinol (PAR), calibração multivariada e técnicas de seleção de variáveis e foi otimizado o empregando-se o algoritmo das projeções sucessivas (APS) e o algoritmo genético (AG), para escolha dos comprimentos de onda mais informativos para a análise. Com essas técnicas, foi possível construir modelos de calibração por regressão linear múltipla (RLM-APS e RLM-AG). Os resultados obtidos foram comparados com modelos de regressão em componentes principais (PCR) e nos mínimos quadrados parciais (PLS). Demonstra-se a partir do erro médio quadrático de previsão (RMSEP) que os modelos apresentam desempenhos semelhantes ao prever as concentrações dos três analitos no medicamento. Todavia os modelos RLM são mais simples pois requerem um número muito menor de comprimentos de onda e são mais fáceis de interpretar que os baseados em variáveis latentes.

First results obtained using the CENBG nanobeam line: performances and applications

A high resolution focused beam line has been recently installed on the AIFIRA (“Applications Interdisciplinaires des Faisceaux d’Ions en Région Aquitaine”) facility at CENBG. This nanobeam line, based on a doublet–triplet configuration of Oxford Microbeam Ltd. OM-50™ quadrupoles, offers the opportunity to focus protons, deuterons and alpha particles in the MeV energy range to a sub-micrometer beam spot. The beam optics design has been studied in detail and optimized using detailed ray-tracing simulations and the full mechanical design of the beam line was reported in the Debrecen ICNMTA conference in 2008. During the last two years, the lenses have been carefully aligned and the target chamber has been fully equipped with particle and X-ray detectors, microscopes and precise positioning stages. The beam line is now operational and has been used for its firstapplications to ion beam analysis. Interestingly, this set-up turned out to be a very versatile tool for a wide range of applications. Indeed, even if it was not intended during the design phase, the ion optics configuration offers the opportunity to work either with a high current microbeam (using the triplet only) or with a lower current beam presenting a sub-micrometer resolution (using the doublet–triplet configuration). The performances of the CENBGnanobeam line are presented for both configurations. Quantitative data concerning the beam lateral resolutions at different beam currents are provided. Finally, the firstresults obtained for different types of application are shown, including nuclear reaction analysis at the micrometer scale and the firstresults on biological samples

Characterization of ultra wideband antennas for personal communication devices using finite difference time domain technique

The current mobile networks don't offer sufficient data rates to support multimedia intensive applications in development for multifunctional mobile devices. Ultra wideband (UWB) wireless technology is being considered as the solution to overcome data rate bottlenecks in the current mobile networks. UWB is able to achieve such high data transmission rates because it transmits data over a very large chunk of the frequency spectrum. As currently approved by the U.S. Federal Communication Commission it utilizes 7.5 GHz of spectrum between 3.1 GHz and 10.6 GHz. ^ Successful transmission and reception of information data using UWB wireless technology in mobile devices, requires an antenna that has linear phase, low dispersion and a voltage standing wave ratio (VSWR) ≤ 2 throughout the entire frequency band. Compatibility with an integrated circuit requires an unobtrusive and electrically small design. The previous techniques that have been used to optimize the performance of UWB wireless systems, involve proper design of source pulses for optimal UWB performance. The goal of this work is directed towards the designing of antennas for personal communication devices, with optimal UWB bandwidth performance. Several techniques are proposed for optimal UWB bandwidth performance of the UWB antenna designs in this Ph.D. dissertation. ^ This Ph.D. dissertation presents novel UWB antenna designs for personal communication devices that have been characterized and optimized using the finite difference time domain (FDTD) technique. The antenna designs reported in this research are physically compact, planar for low profile use, with sufficient impedance bandwidth (>20%), antenna input impedance of 50-Ω, and an omni-directional (±1.5 dB) radiation pattern in the operating bandwidth. ^

Vacuum brazing of alumina ceramic to titanium for biomedical implants using pure gold as the filler metal

One of the many promising applications of metal/ceramic joining is in biomedical implantable devices. This work is focused on vacuum brazing of C.P titanium to 96% alumina ceramic using pure gold as the filler metal. A novel method of brazing is developed where resistance heating of C.P titanium is done inside a thermal evaporator using a Ta heating electrode. The design of electrode is optimized using Ansys resistive heating simulations. The materials chosen in this study are biocompatible and have prior history in implantable devices approved by FDA. This research is part of Boston Retinal implant project to make a biocompatible implantable device (www.bostonretina.org). ^ Pure gold braze has been used in the construction of single terminal feedthrough in low density hermetic packages utilizing a single platinum pin brazed to an alumina or sapphire ceramic donut (brazed to a titanium case or ferrule for many years in implantable pacemakers. Pure gold (99.99%) brazing of 96% alumina ceramic with CP titanium has been performed and evaluated in this dissertation. Brazing has been done by using electrical resistance heating. The 96% alumina ceramic disk was manufactured by high temperature cofired ceramic (HTCC) processing while the Ti ferrule and gold performs were purchased from outside. Hermetic joints having leak rate of the order of 1.6 × 10-8 atm-cc/ sec on a helium leak detector were measured. ^ Alumina ceramics made by HTCC processing were centreless grounded utilizing 800 grit diamond wheel to provide a smooth surface for sputtering of a thin film of Nb. Since pure alumina demonstrates no adhesion or wetting to gold, an adhesion layer must be used on the alumina surface. Niobium (Nb), Tantalum (Ta) and Tungsten (W) were chosen for evaluation since all are refractory (less dissolution into molten gold), all form stable oxides (necessary for adhesion to alumina) and all are readily thin film deposited as metals. Wetting studies are also performed to determine the wetting angle of pure gold to Ti, Ta, Nb and W substrates. Nano tribological scratch testing of thin film of Nb (which demonstrated the best wetting properties towards gold) on polished 96% alumina ceramic is performed to determine the adhesion strength of thin film to the substrate. The wetting studies also determined the thickness of the intermetallic compounds layers formed between Ti and gold, reaction microstructure and the dissolution of the metal into the molten gold.^

High Frequency Class DE Converter Using a Multilayer Coreless PCB Transformer

In modern power electronics equipment, it is desirable to design a low profile, high power density, and fast dynamic response converter. Increases in switching frequency reduce the size of the passive components such as transformers, inductors, and capacitors which results in compact size and less requirement for the energy storage. In addition, the fast dynamic response can be achieved by operating at high frequency. However, achieving high frequency operation while keeping the efficiency high, requires new advanced devices, higher performance magnetic components, and new circuit topology. These are required to absorb and utilize the parasitic components and also to mitigate the frequency dependent losses including switching loss, gating loss, and magnetic loss. Required performance improvements can be achieved through the use of Radio Frequency (RF) design techniques. To reduce switching losses, resonant converter topologies like resonant RF amplifiers (inverters) combined with a rectifier are the effective solution to maintain high efficiency at high switching frequencies through using the techniques such as device parasitic absorption, Zero Voltage Switching (ZVS), Zero Current Switching (ZCS), and a resonant gating. Gallium Nitride (GaN) device technologies are being broadly used in RF amplifiers due to their lower on- resistance and device capacitances compared with silicon (Si) devices. Therefore, this kind of semiconductor is well suited for high frequency power converters. The major problems involved with high frequency magnetics are skin and proximity effects, increased core and copper losses, unbalanced magnetic flux distribution generating localized hot spots, and reduced coupling coefficient. In order to eliminate the magnetic core losses which play a crucial role at higher operating frequencies, a coreless PCB transformer can be used. Compared to the conventional wire-wound transformer, a planar PCB transformer in which the windings are laid on the Printed Board Circuit (PCB) has a low profile structure, excellent thermal characteristics, and ease of manufacturing. Therefore, the work in this thesis demonstrates the design and analysis of an isolated low profile class DE resonant converter operating at 10 MHz switching frequency with a nominal output of 150 W. The power stage consists of a class DE inverter using GaN devices along with a sinusoidal gate drive circuit on the primary side and a class DE rectifier on the secondary side. For obtaining the stringent height converter, isolation is provided by a 10-layered coreless PCB transformer of 1:20 turn’s ratio. It is designed and optimized using 3D Finite Element Method (FEM) tools and radio frequency (RF) circuit design software. Simulation and experimental results are presented for a 10-layered coreless PCB transformer operating in 10 MHz.

Multi-objective optimization of material model parameters of an adhesive layer by using SPEA2

The usage of multi material structures in industry, especially in the automotive industry are increasing. To overcome the difficulties in joining these structures, adhesives have several benefits over traditional joining methods. Therefore, accurate simulations of the entire process of fracture including the adhesive layer is crucial. In this paper, material parameters of a previously developed meso mechanical finite element (FE) model of a thin adhesive layer are optimized using the Strength Pareto Evolutionary Algorithm (SPEA2). Objective functions are defined as the error between experimental data and simulation data. The experimental data is provided by previously performed experiments where an adhesive layer was loaded in monotonically increasing peel and shear. Two objective functions are dependent on 9 model parameters (decision variables) in total and are evaluated by running two FEsimulations, one is loading the adhesive layer in peel and the other in shear. The original study converted the two objective functions into one function that resulted in one optimal solution. In this study, however, a Pareto frontis obtained by employing the SPEA2 algorithm. Thus, more insight into the material model, objective functions, optimal solutions and decision space is acquired using the Pareto front. We compare the results and show good agreement with the experimental data.

Optimal allocation and sizing of DGs in distribution networks

In this paper, the placement and sizing of Distributed Generators (DG) in distribution networks are determined optimally. The objective is to minimize the loss and to improve the reliability. The constraints are the bus voltage, feeder current and the reactive power flowing back to the source side. The placement and size of DGs are optimized using a combination of Discrete Particle Swarm Optimization (DPSO) and Genetic Algorithm (GA). This increases the diversity of the optimizing variables in DPSO not to be stuck in the local minima. To evaluate the proposed algorithm, the semi-urban 37-bus distribution system connected at bus 2 of the Roy Billinton Test System (RBTS), which is located at the secondary side of a 33/11 kV distribution substation, is used. The results finally illustrate the efficiency of the proposed method.

Prediction model of the buildup of volatile organic compounds on urban roads

A model to predict the buildup of mainly traffic-generated volatile organic compounds or VOCs (toluene, ethylbenzene, ortho-xylene, meta-xylene, and para-xylene) on urban road surfaces is presented. The model required three traffic parameters, namely average daily traffic (ADT), volume to capacity ratio (V/C), and surface texture depth (STD), and two chemical parameters, namely total suspended solid (TSS) and total organic carbon (TOC), as predictor variables. Principal component analysis and two phase factor analysis were performed to characterize the model calibration parameters. Traffic congestion was found to be the underlying cause of traffic-related VOC buildup on urban roads. The model calibration was optimized using orthogonal experimental design. Partial least squares regression was used for model prediction. It was found that a better optimized orthogonal design could be achieved by including the latent factors of the data matrix into the design. The model performed fairly accurately for three different land uses as well as five different particle size fractions. The relative prediction errors were 10–40% for the different size fractions and 28–40% for the different land uses while the coefficients of variation of the predicted intersite VOC concentrations were in the range of 25–45% for the different size fractions. Considering the sizes of the data matrices, these coefficients of variation were within the acceptable interlaboratory range for analytes at ppb concentration levels.

Saturated core high-temperature superconducting fault current limiters as an alternative to conventional series reactors in a distribution grid

Series reactors are used in distribution grids to reduce the short-circuit fault level. Some of the disadvantages of the application of these devices are the voltage drop produced across the reactor and the steep front rise of the transient recovery voltage (TRV), which generally exceeds the rating of the associated circuit breaker. Simulations were performed to compare the characteristics of a saturated core High-Temperature Superconducting Fault Current Limiter (HTS FCL) and a series reactor. The design of the HTS FCL was optimized using the evolutionary algorithm. The resulting Pareto frontier curve of optimum solution is presented in this paper. The results show that the steady-state impedance of an HTS FCL is significantly lower than that of a series reactor for the same level of fault current limiting. Tests performed on a prototype 11 kV HTS FCL confirm the theoretical results. The respective transient recovery voltages (TRV) of the HTS FCL and an air core reactor of comparable fault current limiting capability are also determined. The results show that the saturated core HTS FCL has a significantly lower effect on the rate of rise of the circuit breaker TRV as compared to the air core reactor. The simulations results are validated with shortcircuit test results.

Hybrid genetic algorithm for elimination of severe stress concentration in railhead ends

This paper presents a computational method for eliminating severe stress concentration at the unsupported railhead ends in rail joints through innovative shape optimization of the contact zone, which is complex due to near field nonlinear contact. With a view to minimizing the computational efforts, hybrid genetic algorithm method coupled with parametric finite element has been developed and compared with the traditional genetic algorithm (GA). The shape of railhead top surface where the wheel contacts nonlinearly was optimized using the hybridized GA method. Comparative study of the optimal result and the search efficiency between the traditional and hybrid GA methods has shown that the hybridized GA provides the optimal shape in fewer computational cycles without losing accuracy. The method will be beneficial to solving complex engineering problems involving contact nonlinearity.

Managing Project Business Development: an Inter-Organizational and Intra-Organizational Perspective (summary section only)

The driving force behind this study is the gap between the reality of the firms engaged in project business and the available studies covering project management and business process development. Previous studies show that project-based organizations were ‘immature’ in terms of the project-management ‘maturity model’, as few firms were found to be optimizing processes. Even within those, very little attention was paid to combine inter-organizational and intra-organizational perspectives. In this study an effort is made to elaborate some thoughts and views on project management, which interrelate firms’ external and internal activities. In line with the integration, the dissertation uses an approach to the management of project-business interdependencies in the networks of actors, activities and resources. Firstly, the study develops an understanding for inter-organizational perspectives by exploring the complementarities of process activities in the basic development of project business. It presents a framework that is elaborated on the basis of the reciprocal interactions of activities within and outside the organization—thus providing a coherent basis for continuous business-process improvement. In addition, the study presents new tools that can be used to develop project-business processes in each of its functional areas. The research demonstrates how project-business activities can be optimized using the right resources at the right time with the right actors and the right actions. The selected five articles included in this dissertation explain the basic framework for the development of project business. Each paper covers various aspects of inter-organizational and intra-organizational perspectives for project management. The study develops a valuable and procedural model for business-process improvement using the Delphi method that can be used not only in academia but also as a guide for practitioners that takes them through a series of well-defined steps when making informed, consistent and efficient changes to their business processes.

Theoretical studies on alpha-helix--DNA interactions

The interaction energies between (Ala)10 and alpha-helix fragment and different nucleotide sequences in right-handed B-form have been optimized using semi-empirical potential energy functions. The energies are calculated for two different orientations of the alpha-helix, viz., when the alpha-helix axis taken in the N----C direction is (i) parallel and (ii) antiparallel to the 5'-3' ascending strand of DNA, proximal to it. When both the DNA molecule as well as the alpha-helix are treated as rigid molecules it is found that a polyalanine alpha-helix has slightly more favourable contacts when it is in the proximity of a four nucleotide sequence of 5'-(N-A-T-N)-3' type, where N is either a purine or a pyrimidine. However, when the two interacting molecules are allowed to undergo local structural variations then the interaction energy appears to be independent of the base sequence confirming the non-specific nature of these interactions.

Electron donor-acceptor complexes of I-2 with diethyl ether and diethyl sulphide. An ab initio MO study

The charge-transfer complexes of I-2 with the n-donors diethyl ether and diethyl sulfide were studied at the Hartree-Fock and MP2 levels. The structures were fully optimized using the 3-21G((*)) basis set as well as with effective core potentials. The calculations consistently yield a C-2v structure for the ether-I-2 complex, but an unsymmetrical form for the sulfide-I-2 complex. A natural bond orbital analysis and the BSSE-corrected complexation energies reveal stronger interactions in the sulfide complex. The computed orbital energies of the monomers and complexes reproduce the trends in experimentally observed vertical ionization potentials.