Extraction of hemoglobin with calixarenes and biocatalysis in organic media of the complex with pseudoactivity of peroxidase

The present work involves the use of p-tert-butylcalix[4,6,8]arene carboxylic acid derivatives ((t)Butyl[4,6,8]CH2COOH) for selective extraction of hemoglobin. All three calixarenes extracted hemoglobin into the organic phase, exhibiting extraction parameters higher than 0.90. Evaluation of the solvent accessible positively charged amino acid side chains of hemoglobin (PDB entry 1XZ2) revealed that there are 8 arginine, 44 lysine and 30 histidine residues on the protein surface which may be involved in the interactions with the calixarene molecules. The hemoglobin-(t)Butyl[6]CH2COOH complex had pseudoperoxidase activity which catalysed the oxidation of syringaldazine in the presence of hydrogen peroxide in organic medium containing chloroform. The effect of pH, protein and substrate concentrations on biocatalysis was investigated using the hemoglobin-(t)Butyl[6]CH2COOH complex. This complex exhibited the highest specific activity of 9.92 x 10(-2) U mg protein(-1) at an initial pH of 7.5 in organic medium. Apparent kinetic parameters (V'(max), K'(m), k'(cat) and k'(cat)/K'(m)) for the pseudoperoxidase activity were determined in organic media for different pH values from a Michaelis-Menten plot. Furthermore, the stability of the protein-calixarene complex was investigated for different initial pH values and half-life (t(1/2)) values were obtained in the range of 1.96 and 2.64 days. Hemoglobin-calixarene complex present in organic medium was recovered in fresh aqueous solutions at alkaline pH, with a recovery of pseudoperoxidase activity of over 100%. These results strongly suggest that the use of calixarene derivatives is an alternative technique for protein extraction and solubilisation in organic media for biocatalysis.

Introdução ao estudo de durabilidade do betão auto-compactável

O âmbito desta dissertação centra-se na temática de estudos de durabilidade do betão auto-compactavel (BAC), cujo cálculo dos constituintes foi feito pelo método de Nepomuceno. Sobre amostras de 40, 55 e 70 MPa, produzidas segundo o método atrás identificado, foram feitos estudos químicos e morfológicos, de propriedades de transporte de mecanismos de degradação e de propriedades indirectas. Os três provetes em estudo de 40, 55 e 70 MPa, apresentam características satisfatórias a nível da microestrutura, propriedades de transporte, carbonatação, penetração de cloretos e análise de ultra-sons. Numa análise comparativa entre as três resistências mecânicas em estudo, verifica-se que as propriedades de durabilidade vão melhorando a medida que a resistência mecânica também aumenta, ou seja, os provete com 70 MPa apresentam as melhores características a nível de durabilidade e os de 40 as piores; os de 55 apresentam propriedades intermédias.

Internacionalização do vinho do Porto – estudo de caso Grupo Sogevinus

Dissertação apresentada ao Instituto Superior de Contabilidade para a obtenção do Grau de Mestre em Empreendedorismo e Internacionalização Orientada por Professor Doutor José Freitas Santos

Complexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidation

Reactions of copper(II) with 3-phenylhydrazopentane-2,4-diones X-2-C6H4-NHN = C{C(= O)CH3}(2) bearing a substituent in the ortho-position [X = OH (H2L1) 1, AsO3H2 (H3L2) 2, Cl (HL3) 3, SO3H (H2L4) 4, COOCH3 (HL5) 5, COOH (H2L6) 6, NO2 (HL7) 7 or H (HL8) 8] lead to a variety of complexes including the monomeric [CuL4(H2O)(2)]center dot H2O 10, [CuL4(H2O)(2)] 11 and [Cu(HL4)(2)(H2O)(4)] 12, the dimeric [Cu-2(H2O)(2)(mu-HL2)(2)] 9 and the polymeric [Cu(mu-L-6)](n)] 13 ones, often bearing two fused six-membered metallacycles. Complexes 10-12 can interconvert, depending on pH and temperature, whereas the Cu(II) reactions with 4 in the presence of cyanoguanidine or imidazole (im) afford the monomeric compound [Cu(H2O)(4){NCNC(NH2)(2)}(2)](HL4)(2)center dot 6H(2)O 14 and the heteroligand polymer [Cu(mu-L-4)(im)](n) 15, respectively. The compounds were characterized by single crystal X-ray diffraction (complexes), electrochemical and thermogravimetric studies, as well as elemental analysis, IR, H-1 and C-13 NMR spectroscopies (diones) and ESI-MS. The effects of the substituents in 1-8 on the HOMO-LUMO gap and the relative stability of the model compounds [Cu(OH)(L-8)(H2O)]center dot H2O, [Cu(L-1)(H2O)(2)]center dot H2O and [Cu(L-4)(H2O)(2)]center dot H2O are discussed on the basis of DFT calculations that show the stabilization follows the order: two fused 6-membered > two fused 6-membered/5-membered > one 6-membered metallacycles. Complexes 9, 10, 12 and 13 act as catalyst precursors for the peroxidative oxidation (with H2O2) of cyclohexane to cyclohexanol and cyclohexanone, in MeCN/H2O (total yields of ca. 20% with TONs up to 566), under mild conditions.

Energy resource scheduling considering reactive power management

The reactive power management is an important task in future power systems. The control of reactive power allows the increase of distributed energy resources penetration as well as the optimal operation of distribution networks. Currently, the control of reactive power is only controlled in large power units and in high and very high voltage substations. In this paper a reactive power control in smart grids paradigm is proposed, considering the management of distributed energy resources and of the distribution network by an aggregator namely Virtual Power Player (VPP).

Particle swarm optimization based approaches to vehicle-to-grid scheduling

This paper addresses the problem of energy resources management using modern metaheuristics approaches, namely Particle Swarm Optimization (PSO), New Particle Swarm Optimization (NPSO) and Evolutionary Particle Swarm Optimization (EPSO). The addressed problem in this research paper is intended for aggregators’ use operating in a smart grid context, dealing with Distributed Generation (DG), and gridable vehicles intelligently managed on a multi-period basis according to its users’ profiles and requirements. The aggregator can also purchase additional energy from external suppliers. The paper includes a case study considering a 30 kV distribution network with one substation, 180 buses and 90 load points. The distribution network in the case study considers intense penetration of DG, including 116 units from several technologies, and one external supplier. A scenario of 6000 EVs for the given network is simulated during 24 periods, corresponding to one day. The results of the application of the PSO approaches to this case study are discussed deep in the paper.

Intelligent management of end consumers loads including electric vehicles through a SCADA system

The large penetration of intermittent resources, such as solar and wind generation, involves the use of storage systems in order to improve power system operation. Electric Vehicles (EVs) with gridable capability (V2G) can operate as a means for storing energy. This paper proposes an algorithm to be included in a SCADA (Supervisory Control and Data Acquisition) system, which performs an intelligent management of three types of consumers: domestic, commercial and industrial, that includes the joint management of loads and the charge/discharge of EVs batteries. The proposed methodology has been implemented in a SCADA system developed by the authors of this paper – the SCADA House Intelligent Management (SHIM). Any event in the system, such as a Demand Response (DR) event, triggers the use of an optimization algorithm that performs the optimal energy resources scheduling (including loads and EVs), taking into account the priorities of each load defined by the installation users. A case study considering a specific consumer with several loads and EVs is presented in this paper.

Electric vehicles in urban areas: test cases using a scenario simulator

Electric vehicles introduction will affect cities environment and urban mobility policies. Network system operators will have to consider the electric vehicles in planning and operation activities due to electric vehicles’ dependency on the electricity grid. The present paper presents test cases using an Electric Vehicle Scenario Simulator (EVeSSi) being developed by the authors. The test cases include two scenarios considering a 33 bus network with up to 2000 electric vehicles in the urban area. The scenarios consider a penetration of 10% of electric vehicles (200 of 2000), 30% (600) and 100% (2000). The first scenario will evaluate network impacts and the second scenario will evaluate CO2 emissions and fuel consumption.

Intelligent electric vehicle heuristic for energy resource management using simulated annealing

The smart grid concept appears as a suitable solution to guarantee the power system operation in the new electricity paradigm with electricity markets and integration of large amounts of Distributed Energy Resources (DERs). Virtual Power Player (VPP) will have a significant importance in the management of a smart grid. In the context of this new paradigm, Electric Vehicles (EVs) rise as a good available resource to be used as a DER by a VPP. This paper presents the application of the Simulated Annealing (SA) technique to solve the Energy Resource Management (ERM) of a VPP. It is also presented a new heuristic approach to intelligently handle the charge and discharge of the EVs. This heuristic process is incorporated in the SA technique, in order to improve the results of the ERM. The case study shows the results of the ERM for a 33-bus distribution network with three different EVs penetration levels, i. e., with 1000, 2000 and 3000 EVs. The results of the proposed adaptation of the SA technique are compared with a previous SA version and a deterministic technique.

Synthesis and structural characterization of iron complexes with 2,2,2-tris(1-pyrazolyl)ethanol ligands: Application in the peroxidative oxidation of cyclohexane under mild conditions

The reactions of FeCl2 center dot 2H(2)O and 2,2,2-tris(1-pyrazolyl) ethanol HOCH2C(pz)(3) (1) (pz = pyrazolyl) afford [Fe{HOCH2C(pz)(3)}(2)][FeCl4]Cl (2), [Fe{HOCH2C(pz)(3)}(2)](2)[Fe2OCl6](Cl)(2)center dot 4H(2)O (3 center dot 4H(2)O), [Fe{HOCH2C(pz)(3)}(2)] [FeCl{HOCH2C(pz)(3)}(H2O)(2)](2)(Cl)(4) (4) or [Fe{HOCH2C(pz)(3)}(2)]Cl-2 (5), depending on the experimental conditions. Compounds 1-5 were isolated as air-stable crystalline solids and fully characterized, including (1-4) by single-crystal X-ray diffraction analyses. The latter technique revealed strong intermolecular H-bonds involving the OH group of the scorpionate 2 and 3 giving rise to 1D chains which, in 3, are further expanded to a 2D network with intercalated infinite and almost plane chains of H-interacting water molecules. In 4, intermolecular pi center dot center dot center dot pi interactions involving the pyrazolyl rings are relevant. Complexes 2-5 display a high solubility in water (S-25 degrees C ca. 10-12 mg mL(-1)), a favourable feature towards their application as catalysts (or catalyst precursors) for the peroxidative oxidation of cyclo-hexane to cyclohexanol and cyclohexanone, with aqueous H2O2/MeCN, at room temperature (TON values up to ca. 385). (C) 2011 Elsevier B. V. All rights reserved.

An integrated approach for distributed energy resource short term scheduling in smart grids considering realistic power system simulation

The large increase of distributed energy resources, including distributed generation, storage systems and demand response, especially in distribution networks, makes the management of the available resources a more complex and crucial process. With wind based generation gaining relevance, in terms of the generation mix, the fact that wind forecasting accuracy rapidly drops with the increase of the forecast anticipation time requires to undertake short-term and very short-term re-scheduling so the final implemented solution enables the lowest possible operation costs. This paper proposes a methodology for energy resource scheduling in smart grids, considering day ahead, hour ahead and five minutes ahead scheduling. The short-term scheduling, undertaken five minutes ahead, takes advantage of the high accuracy of the very-short term wind forecasting providing the user with more efficient scheduling solutions. The proposed method uses a Genetic Algorithm based approach for optimization that is able to cope with the hard execution time constraint of short-term scheduling. Realistic power system simulation, based on PSCAD , is used to validate the obtained solutions. The paper includes a case study with a 33 bus distribution network with high penetration of distributed energy resources implemented in PSCAD .

Structural characterization and immunogenicity in wildtype and immune tolerant mice of degraded recombinant human interferon alpha2b

Purpose - To study the influence of protein structure on the immunogenicity in wildtype and immune tolerant mice of well-characterized degradation products of recombinant human interferon alpha2b (rhIFNα2b). Methods - RhIFNα2b was degraded by metal catalyzed oxidation (M), crosslinking with glutaraldehyde (G), oxidation with hydrogen peroxide (H) and incubation in a boiling water bath (B). The products were characterized with UV absorption, circular dichroism and fluorescence spectroscopy, gel permeation chromatography, reversed-phase HPLC, SDS-PAGE, Western blotting and mass spectrometry. The immunogenicity of the products was evaluated in wildtype mice and in transgenic mice immune tolerant for hIFNα2. Serum antibodies were detected by ELISA or surface plasmon resonance. Results - M-rhIFNα2b contained covalently aggregated rhIFNα2b with three methionines partly oxidized to methionine sulfoxides. G-rhIFNα2b contained covalent aggregates and did not show changes in secondary structure. H-rhIFNα2b was only chemically changed with four partly oxidized methionines. B-rhIFNα2b was largely unfolded and heavily aggregated. Native (N) rhIFNα2b was immunogenic in the wildtype mice but not in the transgenic mice, showing that the latter were immune tolerant for rhIFNα2b. The antirhIFNα2b antibody levels in the wildtype mice depended on the degradation product: M-rhIFNα2b > H-rhIFNα2b ~ N-rhIFNα2b >> B-rhIFNα2b; G-rhIFNα2b did not induce anti-rhIFNα2b antibodies. In the transgenic mice, only M-rhIFNα2b could break the immune tolerance. Conclusions - RhIFNα2b immunogenicity is related to its structural integrity. Moreover, the immunogenicity of aggregated rhIFNα2b depends on the structure and orientation of the constituent protein molecules and/or on the aggregate size.

Intelligent energy resources management in the context of smart grids

Smart grids are envisaged as infrastructures able to accommodate all centralized and distributed energy resources (DER), including intensive use of renewable and distributed generation (DG), storage, demand response (DR), and also electric vehicles (EV), from which plug-in vehicles, i.e. gridable vehicles, are especially relevant. Moreover, smart grids must accommodate a large number of diverse types or players in the context of a competitive business environment. Smart grids should also provide the required means to efficiently manage all these resources what is especially important in order to make the better possible use of renewable based power generation, namely to minimize wind curtailment. An integrated approach, considering all the available energy resources, including demand response and storage, is crucial to attain these goals. This paper proposes a methodology for energy resource management that considers several Virtual Power Players (VPPs) managing a network with high penetration of distributed generation, demand response, storage units and network reconfiguration. The resources are controlled through a flexible SCADA (Supervisory Control And Data Acquisition) system that can be accessed by the evolved entities (VPPs) under contracted use conditions. A case study evidences the advantages of the proposed methodology to support a Virtual Power Player (VPP) managing the energy resources that it can access in an incident situation.

A data-mining based methodology for wind forecasting

In many countries the use of renewable energy is increasing due to the introduction of new energy and environmental policies. Thus, the focus on the efficient integration of renewable energy into electric power systems is becoming extremely important. Several European countries have already achieved high penetration of wind based electricity generation and are gradually evolving towards intensive use of this generation technology. The introduction of wind based generation in power systems poses new challenges for the power system operators. This is mainly due to the variability and uncertainty in weather conditions and, consequently, in the wind based generation. In order to deal with this uncertainty and to improve the power system efficiency, adequate wind forecasting tools must be used. This paper proposes a data-mining-based methodology for very short-term wind forecasting, which is suitable to deal with large real databases. The paper includes a case study based on a real database regarding the last three years of wind speed, and results for wind speed forecasting at 5 minutes intervals.

Towards a future SCADA

Currently, Power Systems (PS) already accommodate a substantial penetration of DG and operate in competitive environments. In the future PS will have to deal with largescale integration of DG and other distributed energy resources (DER), such as storage means, and provide to market agents the means to ensure a flexible and secure operation. This cannot be done with the traditional PS operation. SCADA (Supervisory Control and Data Acquisition) is a vital infrastructure for PS. Current SCADA adaptation to accommodate the new needs of future PS does not allow to address all the requirements. In this paper we present a new conceptual design of an intelligent SCADA, with a more decentralized, flexible, and intelligent approach, adaptive to the context (context awareness). Once a situation is characterized, data and control options available to each entity are re-defined according to this context, taking into account operation normative and a priori established contracts. The paper includes a case-study of using future SCADA features to use DER to deal with incident situations, preventing blackouts.