Vanadium complexes: recent progress in oxidation catalysis

Oxidovanadium complexes and, to a less extent, some non-oxido ones, are widely used as catalysts or catalyst precursors for various oxidative catalytic reactions by H2O2, (BuOOH)-Bu-t or O-2 under mild conditions. Oxidation reactions (oxidation of alkanes and alcohols, epoxidation of alkenes and allylic alcohols, oxidative bromination, sulfoxidation and oxidative Strecker reactions) of organic compounds are the most relevant ones and are reviewed considering the recent advances in the last five years (2010-2014). The main types of both homogeneous and supported vanadium catalysts and the most efficient catalytic systems in the different reactions are presented and compared. The proposed mechanisms of various catalytic oxidation processes are also outlined. (C) 2015 Elsevier B.V. All rights reserved.

Novel Scorpionate and Pyrazole Dioxovanadium Complexes, Catalysts for Carboxylation and Peroxidative Oxidation of Alkanes

The dioxovanadium(V) complexes [VO2(3,5-Me(2)Hpz)(3)][BF4] (1) (pz = pyrazolyl), [VO2{SO3C(pz)(3)}] (2), [VO2{HB(3,5-Me(2)pz)(3)}] (3) and [VO2{HC(pz)(3)}][BF4] (4), bearing pyrazole or scorpionate ligands, were obtained by reaction of triethyl vanadate [VO(OEt)(3)] with hydrotris(3,5-dimethyl-1-pyrazolyl)methane [HC(3,5-Me(2)pz)(3)] or 3,5-dimethylpyrazole (3,5-Me(2)Hpz; 1), lithium tris(1-pyrazolyl)methanesulfonate {Li[SO3C(pz)(3)], 2}, potassium hydrotris(3,5-dimethyl-1-pyrazolyl)borate {K[HB(3,5-Me(2)pz)(3)], 3} and hydrotris(1-pyrazolyl)methane [HC(pz)(3), 4], respectively. Treatment of [VO(OEt)(3)] with potassium hydrotris(1-pyrazolyl)borate {K[HB(pz)(3)]} led to the mixed eta(3)-tris(pyrazolyl)borate and eta(2)-bis(pyrazolyl)borate oxovanadium(IV) complex [VO{HB(pz)(3)}{H2B(pz)(2)}, 5]. The compounds were characterized by elemental analyses, IR, NMR and EPR spectroscopy, FAB and ESI mass spectrometry, cyclic voltammetry and, for 5, also by single crystal X-ray diffraction analysis. All complexes exhibit catalytic activity in the single-pot carboxylation [in trifluoroacetic acid/potassium peroxodisulfate (CF3COOH/K2S2O8)] of gaseous alkanes (methane and ethane) to carboxylic acids (yields up to 40%. TONs up to 157) and in the peroxidative oxidation [in water/acetonitrile (H2O/NCMe)] of liquid alkanes (cyclohexane and cyclopentane) to the corresponding alcohols and ketones (yields up to 24%, TONs up to 117), under mild conditions.

Magma flow, exsolution processes and rock metasomatism in the Great Messejana-Plasencia dyke (Iberian Peninsula)

Magma flow in dykes is still not well understood; some reported magnetic fabrics are contradictory and the potential effects of exsolution and metasomatism processes on the magnetic properties are issues open to debate. Therefore, a long dyke made of segments with different thickness, which record distinct degrees of metasomatism, the Messejana-Plasencia dyke (MPD), was studied. Oriented dolerite samples were collected along several cross-sections and characterized by means of microscopy and magnetic analyses. The results obtained show that the effects of metasomatism on rock mineralogy are important, and that the metasomatic processes can greatly influence anisotropy degree and mean susceptibility only when rocks are strongly affected by metasomatism. Petrography, scanning electron microscopy (SEM) and bulk magnetic analyses show a high-temperature oxidation-exsolution event, experienced by the very early Ti-spinels, during the early stages of magma cooling, which was mostly observed in central domains of the thick dyke segments. Exsolution reduced the grain size of the magnetic carrier (multidomain to single domain transformation), thus producing composite fabrics involving inverse fabrics. These are likely responsible for a significant number of the 'abnormal' fabrics, which make the interpretation of magma flow much more complex. By choosing to use only the 'normal' fabric for magma flow determination, we have reduced by 50 per cent the number of relevant sites. In these sites, the imbrication angle of the magnetic foliation relative to dyke wall strongly suggests flow with end-members indicating vertical-dominated flow (seven sites) and horizontal-dominated flow (three sites).

Design of improved rail-to-rail low-distortion and low-stress switches in advanced CMOS technologies

This paper describes the efficient design of an improved and dedicated switched-capacitor (SC) circuit capable of linearizing CMOS switches to allow SC circuits to reach low distortion levels. The described circuit (SC linearization control circuit, SLC) has the advantage over conventional clock-bootstrapping circuits of exhibiting low-stress, since large gate voltages are avoided. This paper presents exhaustive corner simulation results of a SC sample-and-hold (S/H) circuit which employs the proposed and optimized circuits, together with the experimental evaluation of a complete 10-bit ADC utilizing the referred S/H circuit. These results show that the SLC circuits can reduce distortion and increase dynamic linearity above 12 bits for wide input signal bandwidths.

Aumento de capacidade em sistemas MIMO coordenados para advanced LTE com utilização de repetidores fixos

Com vista a revolucionar o sector das comunicações móveis, muito à custa dos elevados débitos prometidos, a tecnologia LTE recorre a uma técnica que se prevê que seja bastante utilizada nas futuras redes de comunicações móveis: Relaying. Juntamente com esta técnica, o LTE recorre à técnica MIMO, para melhorar a qualidade da transmissão em ambientes hostis e oferecer elevados ritmos de transmissão. No planeamento das próximas redes LTE, o recurso à técnica Relaying é frequente. Esta técnica, tem como objectivo aumentar a cobertura e/ou capacidade da rede, e ainda melhorar o seu desempenho em condições de fronteira de célula. A performance de uma RS depende da sua localização, das condições de propagação do canal rádio a que tanto a RS como o EU estão sujeitos, e ainda da capacidade que a RS tem de receber, processar e reencaminhar a informação. O objectivo da tese é estudar a relação existente entre o posicionamento de uma RS e o seu desempenho. Desta forma, pretende-se concluir qual a posição ideal de uma RS (tanto do tipo AF como SDF). Para além deste estudo, é apresentado um comparativo do desempenho dos modos MIMO TD e OL-SM, onde se conclui em que condições deverão ser utilizados, numa rede LTE equipada com FRSs.

Eliminação do Cr(VI) na fase de neutralização de um efluente industrial proveniente de processos de galvanoplastia

A presente tese teve por base a identificação e resolução de um problema existente no tratamento de efluentes provenientes dos processos de tratamento de superfícies por galvanoplastia, na OGMA – Indústria Aeronáutica de Portugal S.A.. Observou-se a ocorrência, esporádica, de crómio hexavalente, (Cr (VI)), em valor superior ao valor limite de emissão (VLE). Os resultados foram monitorizados e os dados recolhidos no decorrer da actividade de tratamento de efluentes, durante o período de, aproximadamente, 5 anos (2006 a 2011). A recolha de resultados decorreu no âmbito da actividade profissional da mestranda, que, para além da responsabilidade técnica dos processos de galvanoplastia na empresa, é também responsável pelo suporte técnico ao processo de tratamento de efluentes resultantes da actividade de tratamento de superficies por processos de galvanoplastia. A empresa OGMA – Indústria Aeronáutica de Portugal S.A., é uma empresa de actividade aeronáutica dedicada à Fabricação e Manutenção de aeronaves, nomeadamente a prestação de serviços de Manutenção, Revisão e Modernização de, Aeronaves, Motores e Componentes, bem como Fabricação e Montagem de Aeroestruturas. Integrada na OGMA, S.A. encontra-se a área de tratamentos electroquímicos, onde são realizados processos de tratamento de materiais metálicos por electrodeposição, deposição química e conversão química. Desta actividade resulta uma quantidade considerável de efluentes líquidos que necessitam de tratamento adequado previamente à sua descarga em cursos de água. Devido ao tipo de contaminantes que estes efluentes possuem, o tratamento dos mesmos é realizado em várias etapas, passando pela oxidação de cianetos, a redução de cromatos e a neutralização. Posteriormente segue-se uma sedimentação e a remoção de lamas. De modo a garantir um controlo dos parâmetros de descarga dos efluentes tratados, de acordo com a legislação ambiental em vigor, o efluente obtido é analisado periodicamente em laboratório acreditado. Na perspectiva de solucionar o problema em questão, procedeu-se à realização de ensaios experimentais utilizando os efluentes provenientes dos tanques de reacção da redução de cromatos e da oxidação de cianetos da linha com cádmio, com especial incidência na variação dos intervalos de pH recomendados para cada uma das fases do tratamento de efluentes, e observação do comportamento das misturas em termos de presença de Cr (VI), quando sujeitos a variações de pH. Após análise dos dados disponíveis e realização de todos os ensaios, conclui-se que, o processo de oxidação de cianeto da linha com cádmio e o processo de redução de cromatos na mesma linha estão a funcionar adequadamente. Concluiu-se que o reaparecimento de Cr (VI) ocorre devido à existência de hipoclorito de sódio, em excesso, no tanque de oxidação de cianeto que, quando passa para o tanque de neutralização e entra em contacto com o efluente proveniente do tanque de redução de cromatos, oxida parte do crómio trivalente, (Cr (III)), existente, a Cr (VI). Para impedir a ocorrência deste fenómeno separou-se todo o efluente contendo crómio que passou a ser tratado na linha de tratamento de efluentes isenta de cádmio, não entrando assim em contacto com o efluente que contém hipoclorito não reagido, evitando a oxidação do Cr (III) a Cr (VI).

Paleomagnetic study of the Great Foum Zguid dyke (southern Morocco): A positive contact test related to metasomatic processes

When a paleomagnetic pole is sought for in an igneous body, the host rocks should be subjected to a contact test to assure that the determined paleopole has the age of the intrusion. If the contact test is positive, it precludes the possibility that the measured magnetization is a later effect. Therefore, we investigated the variations of the remanent magnetization along cross-sections of rocks hosting the Foum Zguid dyke (southern Morocco) and the dyke itself. A positive contact test was obtained, but it is mainly related with Chemical/Crystalline Remanent Magnetization due to metasomatic processes in the host-rocks during magma intrusion and cooling, and not only with Thermo-Remanent Magnetization as ordinarily assumed in standard studies. Paleomagnetic data obtained within the dyke then reflect the Earth magnetic field during emplacement of this well-dated (196.9 +/- 1.8 Ma) intrusion.

Advanced side information creation techniques and framework for Wyner-Ziv video coding

Recently, several distributed video coding (DVC) solutions based on the distributed source coding (DSC) paradigm have appeared in the literature. Wyner-Ziv (WZ) video coding, a particular case of DVC where side information is made available at the decoder, enable to achieve a flexible distribution of the computational complexity between the encoder and decoder, promising to fulfill novel requirements from applications such as video surveillance, sensor networks and mobile camera phones. The quality of the side information at the decoder has a critical role in determining the WZ video coding rate-distortion (RD) performance, notably to raise it to a level as close as possible to the RD performance of standard predictive video coding schemes. Towards this target, efficient motion search algorithms for powerful frame interpolation are much needed at the decoder. In this paper, the RD performance of a Wyner-Ziv video codec is improved by using novel, advanced motion compensated frame interpolation techniques to generate the side information. The development of these type of side information estimators is a difficult problem in WZ video coding, especially because the decoder only has available some reference, decoded frames. Based on the regularization of the motion field, novel side information creation techniques are proposed in this paper along with a new frame interpolation framework able to generate higher quality side information at the decoder. To illustrate the RD performance improvements, this novel side information creation framework has been integrated in a transform domain turbo coding based Wyner-Ziv video codec. Experimental results show that the novel side information creation solution leads to better RD performance than available state-of-the-art side information estimators, with improvements up to 2 dB: moreover, it allows outperforming H.264/AVC Intra by up to 3 dB with a lower encoding complexity.

Comparison of deposited surface area of airborne ultrafine particles generated from two welding processes

This article describes work performed on the assessment of the levels of airborne ultrafine particles emitted in two welding processes metal-active gas (MAG) of carbon steel and friction-stir welding (FSW) of aluminium in terms of deposited area in alveolar tract of the lung using a nanoparticle surface area monitor analyser. The obtained results showed the dependence from process parameters on emitted ultrafine particles and clearly demonstrated the presence of ultrafine particles, when compared with background levels. The obtained results showed that the process that results on the lower levels of alveolar-deposited surface area is FSW, unlike MAG. Nevertheless, all the tested processes resulted in important doses of ultrafine particles that are to be deposited in the human lung of exposed workers.

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.

Matrix Converter-Based Unified Power-Flow Controllers: Advanced Direct Power Control Method

This paper presents a direct power control (DPC) for three-phase matrix converters operating as unified power flow controllers (UPFCs). Matrix converters (MCs) allow the direct ac/ac power conversion without dc energy storage links; therefore, the MC-based UPFC (MC-UPFC) has reduced volume and cost, reduced capacitor power losses, together with higher reliability. Theoretical principles of direct power control (DPC) based on sliding mode control techniques are established for an MC-UPFC dynamic model including the input filter. As a result, line active and reactive power, together with ac supply reactive power, can be directly controlled by selecting an appropriate matrix converter switching state guaranteeing good steady-state and dynamic responses. Experimental results of DPC controllers for MC-UPFC show decoupled active and reactive power control, zero steady-state tracking error, and fast response times. Compared to an MC-UPFC using active and reactive power linear controllers based on a modified Venturini high-frequency PWM modulator, the experimental results of the advanced DPC-MC guarantee faster responses without overshoot and no steady-state error, presenting no cross-coupling in dynamic and steady-state responses.

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.

Lean thinking: Glass Wall Management

Sendo os desperdícios “Waste” associados à atividade industrial em Portugal e nos mercados globais e os seus custos inerentes, uma das maiores preocupações a todos os níveis de gestão empresarial, a filosofia “Lean” nasce como ajuda e encaminhamento na solução desta problemática. O conceito “Lean”, no que se refere à indústria, desde sempre e até aos dias de hoje, tem uma enorme ênfase, com a adoção deste conceito.Verificam-se bons resultados ao nível da redução de custos, melhoria da qualidade geral dos artigos produzidos, no controlo da produção em geral e é uma poderosa ferramenta no estreitamento da relação entre os diferentes intervenientes da cadeia de valor de determinado produto, sobretudo com fornecedores e com clientes. Com “Lean Management” e “Glass Wall Management”, em ambientes onde as empresas mais avançadas estão a procurar melhorar a sua competitividade através de uma gestão transparente (“Glass Wall Management”), a partir da qual, “toda informação relevante é compartilhada de maneira a que todos entendam a situação”(Suzaki, K, 1993), ganha cada vez mais importância a existência de uma estrutura organizacional que permita esta transparência e a consequente maturidade das empresas. Neste trabalho foram descritos alguns processos de gestão transparente desenvolvidos nos últimos dois anos numa PME portuguesa, aprofundando o processo de gestão transparente vigente e as ferramentas que ajudam a empresa e que na sua globalidade poderão ser extrapoladas a outras PME Portuguesas de modo que a informação importante e relevante seja partilhada por todos os intervenientes na estrutura empresarial, sendo entendida e desenvolvida por todos através de Edições e Revisões aos documentos mais importantes da empresa. Neste estudo foram contactadas vinte e uma PME’S portuguesas de tipologia de produção MTO (Make to Order) do sector dos estofos/mobiliário, e solicitado o preenchimento de um Questionário, tendo como fim em vista, a verificação do uso desta metodologia “Glass Wall Management” à escala empresarial portuguesa e a interpretação do Conceito Geral “Lean” como filosofia de redução de materiais, tempos e custos.

A Hexanuclear Mixed-Valence Oxovanadium(IV,V) Complex as a Highly Efficient Alkane Oxidation Catalyst

The new hexanuclear mixed-valence vanadium complex [V3O3(OEt)(ashz)(2)(mu-OEt)](2) (1) with an N,O-donor ligand is reported. It acts as a highly efficient catalyst toward alkane oxidations by aqueous H2O2. Remarkably, high turnover numbers up to 25000 with product yields of up to 27% (based on alkane) stand for one of the most active systems for such reactions.

Pyrazole or tris(pyrazolyl)ethanol oxo-vanadium(IV) complexes as homogeneous or supported catalysts for oxidation of cyclohexane under mild conditions

The oxovanadium(IV) complexes [VO(acac)(2)(Hpz)].HC(pz)(3) 1.HC(pz)(3) (acac= acetylacetonate, Hpz = pyrazole, pz = pyrazoly1) and [VOCl2{HOCH2C(pz)(3)}] 2 were obtained from reaction of [VO(acac)(2)] with hydrotris(1-pyrazolyl)methane or of VCl(3)with 2,2,2-tris(1-pyrazolyl)ethanol. The compounds were characterized by elemental analysis, IR, Far-IR and EPR spectroscopies, FAB or ESI mass-spectrometry and, for 1, by single crystal X-ray diffraction analysis. 1 and 2 exhibit catalytic activity for the oxidation of cyclohexane to the cyclohexanol and cyclohexanone mixture in homogeneous system (TONS up to 1100) under mild conditions (NCMe, 24h, room temperature) using benzoyl peroxide (BPO), tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide or the urea-hydrogen peroxide adduct (UHP) as oxidants. 1 and 2 were also immobilized on a polydimethylsiloxane membrane (1-PDMS or 2-PDMS) and the systems acted as supported catalysts for the cyclohexane oxidation using the above oxidants (TONs up to 620). The best results were obtained with mCPBA or BP0 as oxidant. The effects of various parameters, such as the amount of catalyst, nitric acid, reaction time, type of oxidant and oxidant-to-catalyst molar ratio, were investigated, for both homogeneous and supported systems. (C) 2012 Elsevier B.V. All rights reserved.