Oxidação eletroquímica de etanol em temperatura ambiente e intermediária: estudo quantitativo das vias reacionais por espectrometria de massas on-line

Na primeira parte do trabalho, foram investigados materiais ativos para eletro-oxidar etanol e acetaldeído seletivos para a rota C2 (Carbono 2) e, também, ativos para eletro-oxidar hidrogênio molecular, visando a aplicação em células a combustível de hidrogênio indireto. Neste tipo de célula, um processador de combustível externo desidrogena o etanol e os produtos desta reação, contendo H2, acetaldeído e, possivelmente, etanol residual, são direcionados para alimentar o ânodo. Neste sentido, o eletrocatalisador anódico pode ser ativo para a eletro-oxidação de etanol residual, bem como acetaldeído, mas este deve catalisar a reação via C2 com o objetivo de evitar a formação de espécies que envenenam a superfície catalítica (CO ou CHx), ou seja, a ligação C-C deve permanecer intacta. Os eletrocatalisadores bimetálicos foram formados por M/Pt/C (onde M = W, Ru ou Sn) e os produtos reacionais foram analisados por DEMS On-line. Os resultados mostraram que Ru/Pt/C e Sn/Pt/C apresentaram maiores taxas de reação global, no entanto, eles não foram seletivos. Por outro lado, W2/Pt3/C foi mais seletivo para a rota C2, dada a não formação de CH4 e CO2. Além disso, este material também foi ativo e estável para a eletro-oxidação de H2, mesmo na presença de acetaldeído, o que o torna um potencial catalisador para aplicação no ânodo de células a combustível de hidrogênio indireto. Na segunda parte do trabalho, o objetivo foi relacionado com o estudo de eletrocatalisadores seletivos para a rota C1 (Carbono 1). A oxidação eletroquímica do etanol e de seus produtos reacionais foram investigados por DEMS on-line em temperatura ambiente e intermediária (245oC). Para temperatura ambiente, utilizou-se solução aquosa de ácido sulfúrico (H2SO4) e, para temperatura intermediária, utilizou-se ácido sólido (CsH2PO4) como eletrólito. Os eletrocatalisadores investigados foram formados por SnOxRuOx-Pt/C e Pt/C. Em temperatura ambiente, os resultados de polarização potenciodinâmica mostraram uma maior atividade eletrocatalítica para o material SnOxRuOx-Pt/C, com eficiência de corrente para formação de CO2 de 15,6% contra 15,2% para Pt/C, sob condições estagnantes, sem controle por transporte de massa. O stripping de resíduos reacionais, após a eletro-oxidação de etanol bulk, sob condições de fluxo, mostraram o acúmulo de espécies com 1 átomo de carbono (CO e CHx) que causam o bloqueio dos sítios ativos e são oxidadas eletroquimicamente somente em mais altos potenciais (ca. 1,0 V). Por outro lado, as curvas de polarização a 245oC mostraram maiores valores de eficiências de correntes para formação de CO2 (45% para Pt/C em ambos potenciais 0,5 V e 0,8 V contra 36% e 50% para SnOxRuOx-Pt/C em 0,5 V e 0,8 V respectivamente) quando comparado com os valores obtidos em temperatura ambiente, mas com atividades similares para SnOxRuOx-Pt/C e Pt/C. Para ambos os eletrocatalisadores, os estudos de espectrometria de massas a 245oC evidenciaram que as rotas eletroquímicas ocorrem em paralelo com rotas puramente químicas, envolvendo catálise heterogênea, de decomposição do etanol, produzindo H2 e CO2 como produtos majoritários.

Effects of Interspecific Gene Flow on the Phenotypic Variance-Covariance Matrix in Lake Victoria Cichlids

Quantitative genetics theory predicts adaptive evolution to be constrained along evolutionary lines of least resistance. In theory, hybridization and subsequent interspecific gene flow may however rapidly change the evolutionary constraints of a population and eventually change its evolutionary potential, but empirical evidence is still scarce. Using closely related species pairs of Lake Victoria cichlids sampled from four different islands with different levels of interspecific gene flow, we tested for potential effects of introgressive hybridization on phenotypic evolution in wild populations. We found that these effects differed among our study species. Constraints measured as the eccentricity of phenotypic variance-covariance matrices declined significantly with increasing gene flow in the less abundant species for matrices that have a diverged line of least resistance. In contrast we find no such decline for the more abundant species. Overall our results suggest that hybridization can change the underlying phenotypic variance-covariance matrix, potentially increasing the adaptive potential of such populations.

An account of the stopping of Daggenham Breach ... Containing also proper rules for performing any the like work: and proposals for rendering the ports of Dover and Dublin ... commodious for entertaining large ships. To which is prefix'd, a plan of the levels which were over-flow'd by the breach.

Bound in old sprinkled calf.

Neutron-mapping polymer flow: Scattering, flow visualization, and molecular theory

Flows of complex fluids need to be understood at both macroscopic and molecular scales, because it is the macroscopic response that controls the fluid behavior, but the molecular scale that ultimately gives rise to rheological and solid-state properties. Here the flow field of an entangled polymer melt through an extended contraction, typical of many polymer processes, is imaged optically and by small-angle neutron scattering. The dual-probe technique samples both the macroscopic stress field in the flow and the microscopic configuration of the polymer molecules at selected points. The results are compared with a recent tube model molecular theory of entangled melt flow that is able to calculate both the stress and the single-chain structure factor from first principles. The combined action of the three fundamental entangled processes of reptation, contour length fluctuation, and convective constraint release is essential to account quantitatively for the rich rheological behavior. The multiscale approach unearths a new feature: Orientation at the length scale of the entire chain decays considerably more slowly than at the smaller entanglement length.

A low-profile dual-band antenna for a wireless LAN access point

The design of dual-band 2.45/5.2 GHz antenna for an acces point of a Wireless Local Area Network (LAN) is presented. The proposed antenna is formed by a Radial Line Slot Array (RLSA) operating at 2.4 GHz and a Microstrip patch working at 5.2 GHz, both featuring circular polarization. The design of this antenna system is accomplished using commercially available Finite Element software. High Frequency Structure Simulator (HFSS) of Ansoft and an in-house developed iteration procedure. The performance of the designed antenna is assessed in terms of return loss (RL), radiation pattern and polarization purity in the two frequency bands.

Development of an oligonucleotide-based SNP detection method on lateral flow strips using hexapet tages

Detection of point mutations or single nucleotide polymorphisms (SNPs) is important in relation to disease susceptibility or detection in pathogens of mutations determining drug resistance or host range. There is an emergent need for rapid detection methods amenable to point-of-care applications. The purpose of this study was to reduce to practice a novel method for SNP detection and to demonstrate that this technology can be used downstream of nucleic acid amplification. The authors used a model system to develop an oligonucleotide-based SNP detection system on nitrocellulose lateral flow strips. To optimize the assay they used cloned sequences of the herpes simplex virus-1 (HSV-1) DNA polymerase gene into which they introduced a point mutation. The assay system uses chimeric polymerase chain reaction (PCR) primers that incorporate hexameric repeat tags ("hexapet tags"). The chimeric sequences allow capture of amplified products to predefined positions on a lateral flow strip. These "hexapet" sequences have minimal cross-reactivity and allow specific hybridization-based capture of the PCR products at room temperature onto lateral flow strips that have been striped with complementary hexapet tags. The allele-specific amplification was carried out with both mutant and wild-type primer sets present in the PCR mix ("competitive" format). The resulting PCR products carried a hexapet tag that corresponded with either a wild-type or mutant sequence. The lateral flow strips are dropped into the PCR reaction tube, and mutant sequence and wild-type sequences diffuse along the strip and are captured at the corresponding position on the strip. A red line indicative of a positive reaction is visible after 1 minute. Unlike other systems that require separate reactions and strips for each target sequence, this system allows multiplex PCR reactions and multiplex detection on a single strip or other suitable substrates. Unambiguous visual discrimination of a point mutation under room temperature hybridization conditions was achieved with this model system in 10 minutes after PCR. The authors have developed a capture-based hybridization method for the detection and discrimination of HSV-1 DNA polymerase genes that contain a single nucleotide change. It has been demonstrated that the hexapet oligonucleotides can be adapted for hybridization on the lateral flow strip platform for discrimination of SNPs. This is the first step in demonstrating SNP detection on lateral flow using the hexapet oligonucleotide capture system. It is anticipated that this novel system can be widely used in point-of-care settings.

Power flow based monetary flow method for electricity transmission and wheeling pricing

This paper proposes a transmission and wheeling pricing method based on the monetary flow tracing along power flow paths: the monetary flow-monetary path method. Active and reactive power flows are converted into monetary flows by using nodal prices. The method introduces a uniform measurement for transmission service usages by active and reactive powers. Because monetary flows are related to the nodal prices, the impacts of generators and loads on operation constraints and the interactive impacts between active and reactive powers can be considered. Total transmission service cost is separated into more practical line-related costs and system-wide cost, and can be flexibly distributed between generators and loads. The method is able to reconcile transmission service cost fairly and to optimize transmission system operation and development. The case study on the IEEE 30 bus test system shows that the proposed pricing method is effective in creating economic signals towards the efficient use and operation of the transmission system. (c) 2005 Elsevier B.V. All rights reserved.

Study of flow behaviour in a three-product cyclone using computational fluid dynamics

Simplicity in design and minimal floor space requirements render the hydrocyclone the preferred classifier in mineral processing plants. Empirical models have been developed for design and process optimisation but due to the complexity of the flow behaviour in the hydrocyclone these do not provide information on the internal separation mechanisms. To study the interaction of design variables, the flow behaviour needs to be considered, especially when modelling the new three-product cyclone. Computational fluid dynamics (CFD) was used to model the three-product cyclone, in particular the influence of the dual vortex finder arrangement on flow behaviour. From experimental work performed on the UG2 platinum ore, significant differences in the classification performance of the three-product cyclone were noticed with variations in the inner vortex finder length. Because of this simulations were performed for a range of inner vortex finder lengths. Simulations were also conducted on a conventional hydrocyclone of the same size to enable a direct comparison of the flow behaviour between the two cyclone designs. Significantly, high velocities were observed for the three-product cyclone with an inner vortex finder extended deep into the conical section of the cyclone. CFD studies revealed that in the three-product cyclone, a cylindrical shaped air-core is observed similar to conventional hydrocyclones. A constant diameter air-core was observed throughout the inner vortex finder length, while no air-core was present in the annulus. (c) 2006 Elsevier Ltd. All rights reserved.

Investigations into a dual band 2.4/5.2GHz antenna for WLAN applications

The design of a dual-band 2.45/5.2 GHz antenna for an access point of a wireless local area network (WLAN) is presented. The proposed antenna is formed by an assembly of a radial line slot array (RLSA) operating at 2.4 GHz and a microstrip patch working at 5.2 GHz. The design of this antenna system is accomplished using commercially available finite element software, high frequency structure simulator (HFSS), of Ansoft. The performance of the designed antenna is assessed in terms of return loss (RL), radiation pattern and polarization purity in the two investigated frequency bands.

First-line therapy with latanoprost 0.005% results in improved ocular circulation in newly diagnosed primary open-angle glaucoma patients: a prospective, 6-month, open-label study

Purpose To evaluate the effect of latanoprost 0.005% on the optic nerve head (ONH) and retinal circulation of newly diagnosed and previously untreated primary open-angle glaucoma (POAG) patients. Methods Twenty-two newly diagnosed and previously untreated POAG patients (mean age±SD: 68.38±11.92 years) were included in this longitudinal open-label study. Patients were treated with latanoprost 0.005% once a day. Intraocular pressure (IOP), systemic blood pressure (BP), mean ocular perfusion pressure (MOPP), and ocular perfusion parameters ‘volume’, ‘velocity’, and ‘flow’ measured at the optic nerve head (ONH) and retina by means of Heidelberg Retina Flowmeter system were evaluated during a 6-month follow-up period. Results Treatment with latanoprost 0.005% resulted in a significant decrease in IOP (P<0.0001) and increase in MOPP (P<0.0001). After correcting for changes in MOPP, the blood velocity measured at the ONH level was significantly higher after 6 months of treatment than at baseline (P=0.0310). In addition, blood volume and flow measured at the peripapillary retina level improved after 3 and 6 months of treatment (P=0.0170; P=0.0260, and P=0.0170; P=0.0240 respectively). Conclusion Previously untreated POAG patients exhibit reduced IOP, increased MOPP and improved ocular perfusion at the ONH and retina levels when treated with Latanoprost 0.005%. These effects could be beneficial for glaucoma patients suffering from ocular vascular dysregulation.

Two way power flow using GTO thyristors

Two-way power flow is nothing new and has been in practical use using line commutated converters for at least 50 years. With these types of converters, reversal of power flow can be achieved by increasing the firing angle of the devices beyond 90 degrees thus producing a negative DC voltage. Line commutated converters have several known disadvantages including: the direct current cannot be reversed, the power factor decreases when the firing angle increases and the harmonics are high on the line current. To tackle the above problems a forced commutated converter can be used. The power factor can be unity and the harmonics can be reduced. Many researchers have used PWM with different control techniques to serve the above purposes. In each converter arm, they used a forced commutated device with an antiparallel diode. Under the rectification mode of operation the current path is preponderantly through the diodes and under the inverter operation the current flows preponderantly through the forced commutated devices. Although their results were encouraging and gave a unity power factor with nearly sinusoidal current, the main disadvantage was that there were difficulties in controlling the power factor when the system is needed to operate at lagging or leading power factor. In this work, a new idea was introduced by connecting two GTOs antiparallel instead of a diode and a GTO. A single phase system using two GTO converters which are connected in series was built. One converter operates as a rectifier and the other converter operates as an inverter. In the case of the inversion mode and in each inverter arm one GTO is operated as a diode simply by switching it always on and the other antiparallel GTO is operated as a normal device to carry the inverter current. In case of the rectification mode, in each arm one GTO is always off and the other GTP is operated as a controlled device. The main advantage is that the system can be operated at lagging or leading power factor.

The mechanical properties and formability of dual-phase steel

In recent years dual phase steels comprising of 5-20% martensite in a ferrite matrix have come into the limelight of high strength cold formable steels because of their potential for vehicle weight saving. They show the following features: no yield point; relatively low initial flow stress; high initial workhardening rate; well sustained work hardening. As a consequence of these characteristics, dual phase steels exhibit a better combination of strength and elongation than other HSLA steels. In this thesis, a broad view of the factors which influence their properties is presented. Mechanical properties and forming ability of a commercially available dual phase steel and an AL-Si killed steel processed to dual phase form are investigated to ascertain the effect of their microstructure on their properties. It is found that the yield phenomena are masked by the transformation induced stresses present during processing and so yield point could be recovered under suitable ageing treatment; that apart from giving the above properties dual phasing gives rise to very low strain-rate sensitivity and a low R value ~ 1; that the mechanical response under rolling conditions is not different from those under tension; that there is a danger of damage to tooling during forming operations of these steels if fracture should precede instability as a result of grain size dependent strength found for these steels. It is also found that very little deformation of the martensite islands took place during deformation except at high strains. The work-hardening and the strength levels can be controlled by either decreasing the grain size or increasing the martensite volume fraction, but it is found that increasing martensite has a detrimental effect on ductility and the ductility and fracture strength can be controlled better by refining the grain size. A remarkable effect found in the dual phase steel tested is that the compressive strength is higher than the tensile strength. The reason for this observation is not yet clear but it is suggested that it might be due to the introduction of emissary type dislocations into the ferrite lattice as a result of twins formed in the martensite during transformation from austenite. The twins are envisaged to be {111} <112> in character.

Complementary methods to investigate the development of clogging within a horizontal sub-surface flow tertiary treatment wetland

A combination of experimental methods was applied at a clogged, horizontal subsurface flow (HSSF) municipal wastewater tertiary treatment wetland (TW) in the UK, to quantify the extent of surface and subsurface clogging which had resulted in undesirable surface flow. The three dimensional hydraulic conductivity profile was determined, using a purpose made device which recreates the constant head permeameter test in-situ. The hydrodynamic pathways were investigated by performing dye tracing tests with Rhodamine WT and a novel multi-channel, data-logging, flow through Fluorimeter which allows synchronous measurements to be taken from a matrix of sampling points. Hydraulic conductivity varied in all planes, with the lowest measurement of 0.1 md1 corresponding to the surface layer at the inlet, and the maximum measurement of 1550 md1 located at a 0.4m depth at the outlet. According to dye tracing results, the region where the overland flow ceased received five times the average flow, which then vertically short-circuited below the rhizosphere. The tracer break-through curve obtained from the outlet showed that this preferential flow-path accounted for approximately 80% of the flow overall and arrived 8 h before a distinctly separate secondary flow-path. The overall volumetric efficiencyof the clogged system was 71% and the hydrology was simulated using a dual-path, dead-zone storage model. It is concluded that uneven inlet distribution, continuous surface loading and high rhizosphere resistance is responsible for the clog formation observed in this system. The average inlet hydraulic conductivity was 2 md1, suggesting that current European design guidelines, which predict that the system will reach an equilibrium hydraulic conductivity of 86 md1, do not adequately describe the hydrology of mature systems.

Apoptotic and necrotic effects of hexanedione derivatives on the human neuroblastoma line SK-N-SH

The potential cytotoxicity of two hexanedione food additives (2,3 and 3,4 isomers) was evaluated in comparison with the neurotoxic hexane metabolite 2,5-hexanedione in the human SK-N-SH neuroblastoma line using the MTT assay to indicate mitochondrial dehydrogenase activity and flow cytometry to monitor the cell cycle over 48 h. The IC50s of the 2,3-hexanedione (3.3 ± 0.1 mM) and 3,4-hexanedione (3.5 ± 0.1 mM), indicated that the sensitivity of the cells was approximately seven-fold greater to these toxins compared with the 2,5 derivative (IC50 of 22.4 ± 0.2 mM). Comparison between the respective IC50s of the 2,3-hexanedione and 3,4-hexanedione revealed no difference between the two isomers in terms of their effects on MTT turnover. With flow cytometry analysis, all three hexanediones showed increases in apoptosis within their respective concentration ranges of toxicity shown previously by MTT. In the presence of 2,5-hexanedione, between 8.5 and 17 mM concentrations, there was a significant increase in apoptotic nucleoids which was accompanied by a significant fall in the percentage of nucleoids in the G0/G1 phase (72.4 ± 0.3-45.3 ± 0.6%,), and a rise in the numbers of cells in the G2/M phase. This is likely to indicate growth arrest at cell cycle G2/M checkpoint in response to toxin damage. G2/M accumulation was also shown with 3,4 and 2,3 HD, which was maximal at much lower concentrations (approximately 4 and 3 mM, respectively). Arrest at G1 and G2/M phase is indicative of inhibition of the cell cycle at the stages of DNA replication and chromosome segregation, respectively. It was also apparent that flow cytometry, rather than the MTT assay, did distinguish between the effects of the α-diketones 2,3-hexanedione and 3,4-hexanedione on the cell cycle. At a concentration of 5.8 mM 3,4-hexanedione, the percentage of apoptotic nucleoids was 10.9 ± 0.8% whilst apoptosis induced by 3,4-hexanedione had already reached a maximal level of 60.4 ± 0.5%. In summary, flow cytometry indicated that the 3,4-hexanedione derivative was more toxic than its 2,3 isomer and that both food additives caused interruption in the neuroblastoma cell cycle and further investigation may be required to assess if these α-diketones present in diets pose any possible risks to human health. © 2006 Elsevier Ireland Ltd. All rights reserved.

Synthesis and characterization of dual-functionalized core-shell fluorescent microspheres for bioconjugation and cellular delivery

The efficient transport of micron-sized beads into cells, via a non-endocytosis mediated mechanism, has only recently been described. As such there is considerable scope for optimization and exploitation of this procedure to enable imaging and sensing applications to be realized. Herein, we report the design, synthesis and characterization of fluorescent microsphere-based cellular delivery agents that can also carry biological cargoes. These core-shell polymer microspheres possess two distinct chemical environments; the core is hydrophobic and can be labeled with fluorescent dye, to permit visual tracking of the microsphere during and after cellular delivery, whilst the outer shell renders the external surfaces of the microspheres hydrophilic, thus facilitating both bioconjugation and cellular compatibility. Cross-linked core particles were prepared in a dispersion polymerization reaction employing styrene, divinylbenzene and a thiol-functionalized co-monomer. These core particles were then shelled in a seeded emulsion polymerization reaction, employing styrene, divinylbenzene and methacrylic acid, to generate orthogonally functionalized core-shell microspheres which were internally labeled via the core thiol moieties through reaction with a thiol reactive dye (DY630-maleimide). Following internal labeling, bioconjugation of green fluorescent protein (GFP) to their carboxyl-functionalized surfaces was successfully accomplished using standard coupling protocols. The resultant dual-labeled microspheres were visualized by both of the fully resolvable fluorescence emissions of their cores (DY630) and shells (GFP). In vitro cellular uptake of these microspheres by HeLa cells was demonstrated conventionally by fluorescence-based flow cytometry, whilst MTT assays demonstrated that 92% of HeLa cells remained viable after uptake. Due to their size and surface functionalities, these far-red-labeled microspheres are ideal candidates for in vitro, cellular delivery of proteins, as described in the accompanying paper.