Oxorhenium Complexes Bearing the Water-Soluble Tris(pyrazol-1-yl)methanesulfonate, 1,3,5-Triaza-7-phosphaadamantane, or Related Ligands, as Catalysts for Baeyer-Villiger Oxidation of Ketones

New rhenium(VII or III) complexes [ReO3(PTA)(2)][ReO4] (1) (PTA = 1,3,5-triaza-7-phosphaadamantane), [ReO3(mPTA)][ReO4] (2) (mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [ReO3(HMT)(2)] [ReO4] (3) (HMT = hexamethylenetetramine), [ReO3(eta(2)-Tpm)(PTA)][ReO4] (4) [Tpm = hydrotris(pyrazol-1-yl)methane, HC(pz)(3), pz = pyrazolyl), [ReO3(Hpz)(HMT)][ReO4] (5) (Hpz = pyrazole), [ReO(Tpms)(HMT)] (6) [Tpms = tris(pyrazol-1-yl)methanesulfonate, O3SC(pz)(3)(-)] and [ReCl2{N2C(O)Ph} (PTA)(3)] (7) have been prepared from the Re(VII) oxide Re2O2 (1-6) or, in the case of 7, by ligand exchange from the benzoyldiazenido complex [ReCl2(N2C-(O)Ph}(Hpz)(PPh3)(2)], and characterized by IR and NMR spectroscopies, elemental analysis and electrochemical properties. Theoretical calculations at the density functional theory (DFT) level of theory indicated that the coordination of PTA to both Re(III) and Re(VII) centers by the P atom is preferable compared to the coordination by the N atom. This is interpreted in terms of the Re-PTA bond energy and hard-soft acid-base theory. The oxo-rhenium complexes 1-6 act as selective catalysts for the Baeyer-Villiger oxidation of cyclic and linear ketones (e.g., 2-methylcyclohexanone, 2-methylcyclopentanone, cyclohexanone, cyclopentanone, cyclobutanone, and 3,3-dimethyl-2-butanone or pinacolone) to the corresponding lactones or esters, in the presence of aqueous H2O2. The effects of a variety of factors are studied toward the optimization of the process.

Analysis and simulation of a-Si Ha-SiC HPINIP structures for color image detection

It is presented in this paper a study on the photo-electronic properties of multi layer a-Si: H/a-SiC: H p-i-n-i-p structures. This study is aimed to give an insight into the internal electrical characteristics of such a structure in thermal equilibrium, under applied Was and under different illumination condition. Taking advantage of this insight it is possible to establish a relation among-the electrical behavior of the structure the structure geometry (i.e. thickness of the light absorbing intrinsic layers and of the internal n-layer) and the composition of the layers (i.e. optical bandgap controlled through percentage of carbon dilution in the a-Si1-xCx: H layers). Showing an optical gain for low incident light power controllable by means of externally applied bias or structure composition, these structures are quite attractive for photo-sensing device applications, like color sensors and large area color image detector. An analysis based on numerical ASCA simulations is presented for describing the behavior of different configurations of the device and compared with experimental measurements (spectral response and current-voltage characteristic). (c) 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

a-SiH p-i-n structures with extreme i-layer thickness

We present measurements and numerical simulation of a-Si:H p-i-n detectors with a wide range of intrinsic layer thickness between 2 and 10 pm. Such a large active layer thickness is required in applications like elementary particle detectors or X-ray detectors. For large thickness and depending on the applied bias, we observe a sharp peak in the spectral response in the red region near 700 nm. Simulation results obtained with the program ASCA are in agreement with the measurement and permit the explanation of the experimental data. In thick samples holes recombine or are trapped before reaching the contacts, and the conduction mechanism is fully electron dominated. As a consequence, the peak position in the spectral response is located near the optical band gap of the a-Si:H i-layer. (C) 2009 Elsevier B.V. All rights reserved.

Subunits of the chaperonin CCT are associated with Tetrahymena microtubule structures and are involved in cilia biogenesis

The cytosolic chaperonin CCT is a heterooligomeric complex of about 900 kDa that mediates the folding of cytoskeletal proteins. We observed by indirect immunofluorescence that the Tetrahymena TpCCTalpha, TpCCTdelta, TpCCTepsilon, and TpCCTeta-subunits colocalize with tubulin in cilia, basal bodies, oral apparatus, and contractile vacuole pores. TpCCT-subunits localization was affected during reciliation. These findings combined with atomic force microscopy measurements in reciliating cells indicate that these proteins play a role during cilia biogenesis related to microtubule nucleation, tubulin transport, and/or axoneme assembly. The TpCCT-subunits were also found to be associated with cortex and cytoplasmic microtubules suggesting that they can act as microtubule-associated proteins. The TpCCTdelta being the only subunit found associated with the macronuclear envelope indicates that it has functions outside of the 900 kDa complex. Tetrahymena cytoplasm contains granular/globular-structures of TpCCT-subunits in close association with microtubule arrays. Studies of reciliation and with cycloheximide suggest that these structures may be sites of translation and folding. Combined biochemical techniques revealed that reciliation affects the oligomeric state of TpCCT-subunits being tubulin preferentially associated with smaller CCT oligomeric species in early stages of reciliation. Collectively, these findings indicate that the oligomeric state of CCT-subunits reflects the translation capacity of the cell and microtubules integrity.

Magnetic and plagioclase linear fabric discrepancy in dykes: a new way to define the flow vector using magnetic foliation

In basaltic dykes the magnetic lineation K1 (maximum magnetic susceptibility axis) is generally taken to indicate the flow direction during solidification of the magma. This assumption was tested in Tertiary basaltic dykes from Greenland displaying independent evidence of subhorizontal flow. The digital processing of microphotographs from thin sections cut in (K1, K2) planes yields the preferred linear orientation of plagioclase, which apparently marks the magma flow lineation. In up to 60% of cases, the angular separation between K1 and the assumed flow direction is greater than 45degrees. This suggests that the uncorroborated use of magnetic lineations in dykes is risky. A simple geometrical method is proposed to infer the flow vector from AMS in dykes based solely on magnetic foliations.

Signal Subspace Identification in Hyperspectral Linear Mixtures

Chpater in Book Proceedings with Peer Review Second Iberian Conference, IbPRIA 2005, Estoril, Portugal, June 7-9, 2005, Proceedings, Part II

Tuneable micro- and nano-periodic structures in urethane/urea networks

Micro- and nano-patterned materials are of great importance for the design of new nanoscale electronic, optical and mechanical devices, ranging from sensors to displays. A prospective system that can support a designed functionality is elastomeric polyurethane thin films with nano- or micromodulated surface structures ("wrinkles"). These wrinkles can be induced on different lengthscales by mechanically stretching the films, without the need for any sophisticated lithographic techniques. In the present article we focus on the experimental control of the wrinkling process. A simple model for wrinkle formation is also discussed, and some preliminary results reported. Hierarchical assembly of these tunable structures paves the way for the development of a new class of materials with a wide range of applications, from electronics to biomedicine.

Thermal Residual Stresses in Functionally Graded Structures: a Didactic Case Study

Conferência: 2nd Experiment at International Conference - 18-20 September 2013

Assessment of data-driven modeling strategies for water delivery canals

The aim of this paper is to develop models for experimental open-channel water delivery systems and assess the use of three data-driven modeling tools toward that end. Water delivery canals are nonlinear dynamical systems and thus should be modeled to meet given operational requirements while capturing all relevant dynamics, including transport delays. Typically, the derivation of first principle models for open-channel systems is based on the use of Saint-Venant equations for shallow water, which is a time-consuming task and demands for specific expertise. The present paper proposes and assesses the use of three data-driven modeling tools: artificial neural networks, composite local linear models and fuzzy systems. The canal from Hydraulics and Canal Control Nucleus (A parts per thousand vora University, Portugal) will be used as a benchmark: The models are identified using data collected from the experimental facility, and then their performances are assessed based on suitable validation criterion. The performance of all models is compared among each other and against the experimental data to show the effectiveness of such tools to capture all significant dynamics within the canal system and, therefore, provide accurate nonlinear models that can be used for simulation or control. The models are available upon request to the authors.

Controlo e optimização de sistemas AVAC recorrendo a técnicas de inteligência artificial

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

Linear and sliding-mode control design for matrix converter-based unified power flow controllers

This paper presents the design and compares the performance of linear, decoupled and direct power controllers (DPC) for three-phase matrix converters operating as unified power flow controllers (UPFC). A simplified steady-state model of the matrix converter-based UPFC fitted with a modified Venturini high-frequency pulse width modulator is first used to design the linear controllers for the transmission line active (P) and reactive (Q) powers. In order to minimize the resulting cross coupling between P and Q power controllers, decoupled linear controllers (DLC) are synthesized using inverse dynamics linearization. DPC are then developed using sliding-mode control techniques, in order to guarantee both robustness and decoupled control. The designed P and Q power controllers are compared using simulations and experimental results. Linear controllers show acceptable steady-state behaviour but still exhibit coupling between P and Q powers in transient operation. DLC are free from cross coupling but are parameter sensitive. Results obtained by DPC show decoupled power control with zero error tracking and faster responses with no overshoot and no steady-state error. All the designed controllers were implemented using the same digital signal processing hardware.

In vitro assessment of three dimensional dense chitosan-based structures to be as bioabsorbable implants

Chitosan biocompatibility and biodegradability properties make this biopolymer promising for the development of advanced internal fixation devices for orthopedic applications. This work presents a detailed study on the production and characterization of three dimensional (3D) dense, non-porous, chitosan-based structures, with the ability to be processed in different shapes, and also with high strength and stiffness. Such features are crucial for the application of such 3D structures as bioabsorbable implantable devices. The influence of chitosan's molecular weight and the addition of one plasticizer (glycerol) on 3D dense chitosan-based products' biomechanical properties were explored. Several specimens were produced and in vitro studies were performed in order to assess the cytotoxicity of these specimens and their physical behavior throughout the enzymatic degradation experiments. The results point out that glycerol does not impact on cytotoxicity and has a high impact in improving mechanical properties, both elasticity and compressive strength. In addition, human mesenchymal stem/stromal cells (MSC) were used as an ex-vivo model to study cell adhesion and proliferation on these structures, showing promising results with fold increase values in total cell number similar to the ones obtained in standard cell culture flasks. (C) 2014 Elsevier Ltd. All rights reserved.

On the use of particle swarm optimization to maximize bending stiffness of functionally graded structures

Functionally graded materials are a type of composite materials which are tailored to provide continuously varying properties, according to specific constituent's mixing distributions. These materials are known to provide superior thermal and mechanical performances when compared to the traditional laminated composites, because of this continuous properties variation characteristic, which enables among other advantages, smoother stresses distribution profiles. Therefore the growing trend on the use of these materials brings together the interest and the need for getting optimum configurations concerning to each specific application. In this work it is studied the use of particle swarm optimization technique for the maximization of a functionally graded sandwich beam bending stiffness. For this purpose, a set of case studies is analyzed, in order to enable to understand in a detailed way, how the different optimization parameters tuning can influence the whole process. It is also considered a re-initialization strategy, which is not a common approach in particle swarm optimization as far as it was possible to conclude from the published research works. As it will be shown, this strategy can provide good results and also present some advantages in some conditions. This work was developed and programmed on symbolic computation platform Maple 14. (C) 2013 Elsevier B.V. All rights reserved.

Optimal location of supports in beam structures using genetic algorithms

Real structures can be thought as an assembly of components, as for instances plates, shells and beams. This later type of component is very commonly found in structures like frames which can involve a significant degree of complexity or as a reinforcement element of plates or shells. To obtain the desired mechanical behavior of these components or to improve their operating conditions when rehabilitating structures, one of the eventual parameters to consider for that purpose, when possible, is the location of the supports. In the present work, a beam-type structure is considered, and for a set of cases concerning different number and types of supports, as well as different load cases, the authors optimize the location of the supports in order to obtain minimum values of the maximum transverse deflection. The optimization processes are carried out using genetic algorithms. The results obtained, clearly show a good performance of the approach proposed. © 2014 IEEE.

Optimization of magneto-electro-elastic composite structures using differential evolution

Magneto-electro-elastic structures are built from materials that provide them the ability to convert in an interchangeable way, magnetic, electric and mechanical forms of energy. This characteristic can therefore provide an adaptive behaviour to a general configuration elastic structure, being commonly used in association with any type of composite material in an embedded or surface mounted mode, or by considering the usage of multiphase materials that enable achieving different magneto-electro-elastic properties. In a first stage of this work, a few cases studies will be considered to enable the validation of the model considered and the influence of the coupling characteristics of this type of adaptive structures. After that we consider the application of a recent computational intelligence technique, the differential evolution, in a deflection profile minimization problem. Studies on the influence of optimization parameters associated to the problem considered will be performed as well as the adoption of an adaptive scheme for the perturbation factor. Results are also compared with those obtained using an enhanced particle swarm optimization technique. (C) 2013 Elsevier Ltd. All rights reserved.