Mono(Eta(5)-cyclopentadienyl)metal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies, and first hyperpolarizabilities

A series of mono(eta(5)-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta(5)-C5H5)(L)(C C{C4H2S}(n)NO2)] (M = Fe, L = kappa(2)-DPPE, n = 1,2; M = Ru, L = kappa(2)-DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV-Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push pull systems.

Mu-Chlorido-Bridged Dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.

The solvation and electrochemical behaviour of Copper acetylacetonate complexes in ionic liquids

The behavior of copper(II) complexes of pentane-2,4-dione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, [Cu(acac)(2) (1) and [Cu(HFacac)(2)(H2O)] (2), in ionic liquids and molecular organic solvents, was studied by spectroscopic and electrochemical techniques. The electron paramagnetic resonance characterization (EPR) showed well-resolved spectra in most solvents. In general the EPR spectra of [Cu(acac)(2)] show higher g(z) values and lower hyperfine coupling constants, A(z), in ionic liquids than in organic solvents, in agreement with longer Cu-O bond lengths and higher electron charge in the copper ion in the ionic liquids, suggesting coordination of the ionic liquid anions. For [Cu(HFacac)(2)(H2O)] the opposite was observed suggesting that in ionic liquids there is no coordination of the anions and that the complex is tetrahedrically distorted. The redox properties of the Cu(II) complexes were investigated by cyclic voltammetry (CV) at a Pt electrode (d = 1 mm), in bmimBF(4) and bmimNTf(2) ionic liquids and, for comparative purposes, in neat organic solvents. The neutral copper(II) complexes undergo irreversible reductions to Cu(I) and Cu(0) species in both ILs and common organic solvents (CH2Cl2 or acetonitrile), but, in ILs, they are usually more easier to reduce (less cathodic reduction potential) than in the organic solvents. Moreover, 1 and 2 are easier to reduce in bmimNTf(2) than in bmimBF(4) ionic liquid. (C) 2013 Elsevier B.V. All rights reserved.

µ-Chlorido-bridged dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisiloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.

The importance to update the guidelines for the use of genetic testing in noncancer patients in Brazil

The Brazilian National Regulatory Agency for Private Health Insurance and Plans has recently published a technical note defining the criteria for the coverage of genetic testing to diagnose hereditary cancer. In this study we show the case of a patient with a breast lesion and an extensive history of cancer referred to a private service of genetic counseling. The patient met both criteria for hereditary breast and colorectal cancer syndrome screening. Her private insurance denied coverage for genetic testing because she lacks current or previous cancer diagnosis. After she appealed by lawsuit, the court was favorable and the test was performed using next-generation sequencing. A deletion of MLH1 exon 8 was found. We highlight the importance to offer genetic testing using multigene analysis for noncancer patients.

Acylated cyanoimido-complexes trans-[Mo(NCN){NCN(O)R}(DPPE)(2)]Cl and their reactons with electrophiles: Chemical, electrochemical and theoretical study

Treatment of a dichloromethane solution of trans-[Mo(NCN){NCNC(O)R}(dppe)(2)]Cl [R = Me (1a), Et (1b)] (dppe = Ph2PCH2CH2PPh2) with HBF4, [Et3O][BF4] or EtC(O)Cl gives trans-[Mo(NCN)Cl-(dppe)(2)]X [X = BF4 (2a) or Cl (2b)] and the corresponding acylcyanamides NCN(R')C(O)Et (R' = H, Et or C(O)Et). X-ray diffraction analysis of 2a (X = BF4) reveals a multiple-bond coordination of the cyanoimide ligand. Compounds 1 convert to the bis(cyanoimide) trans-[Mo(NCN)(2)(dppe)(2)] complex upon reaction with an excess of NaOMe (with formation of the respective ester). In an aprotic medium and at a Pt electrode, compounds 1 (R = Me, Et or Ph) undergo a cathodically induced isomerization. Full quantitative kinetic analysis of the voltammetric behaviour is presented and allows the determination of the first-order rate constants and the equilibrium constant of the trans to cis isomerization reaction. The mechanisms of electrophilic addition (protonation) to complexes 1 and the precursor trans[Mo(NCN)(2)(dppe)(2)], as well as the electronic structures, nature of the coordination bonds and electrochemical behaviour of these species are investigated in detail by theoretical methods which indicate that the most probable sites of the proton attack are the oxygen atom of the acyl group and the terminal nitrogen atom, respectively.

Electrochemical and analytical investigation of passive films formed on stainless steels in alkaline media

Passive films were grown in potentiodynamic mode, by cyclic voltammetry on AISI 316 and AISI 304 stainless steels. The composition of these films was investigated by X-ray photoelectron spectroscopy (XPS). The electrochemical behaviour and the chemical composition of the passive films formed by cyclic voltammetry were compared to those of films grown under natural conditions (by immersion at open circuit potential, OCP) in alkaline solutions simulating concrete. The study included the effect of pH of the electrolyte and the effect of the presence of chloride ions. The XPS results revealed important changes in the passive film composition, which becomes enriched in chromium and depleted in magnetite as the pH decreases. On the other hand, the presence of chlorides promotes a more oxidised passive layer. The XPS results also showed relevant differences on the composition of the oxide layers for the films formed under cyclic voltammetry and/or under OCP.

Evaluation of the influence of testing parameters on the melt flow index of thermoplastics

The main goals of the present work are the evaluation of the influence of several variables and test parameters on the melt flow index (MFI) of thermoplastics, and the determination of the uncertainty associated with the measurements. To evaluate the influence of test parameters on the measurement of MFI the design of experiments (DOE) approach has been used. The uncertainty has been calculated using a "bottom-up" approach given in the "Guide to the Expression of the Uncertainty of Measurement" (GUM). Since an analytical expression relating the output response (MFI) with input parameters does not exist, it has been necessary to build mathematical models by adjusting the experimental observations of the response variable in accordance with each input parameter. Subsequently, the determination of the uncertainty associated with the measurement of MFI has been performed by applying the law of propagation of uncertainty to the values of uncertainty of the input parameters. Finally, the activation energy (Ea) of the melt flow at around 200 degrees C and the respective uncertainty have also been determined.

Testing native speakers of German and Portuguese on the understanding of topological operators-line-region relations in gvSIG

Dissertation submitted in partial fulfilment of the requirements for the Degree of Master of Science in Geospatial Technologies

Design and testing of a radiation hardened 13-bit 80 MS/s pipeline ADC implemented in a 90nm standard CMOS process

Second International Workshop on Analog and Mixed Signal Integrated Circuits for Space Applications (AMICSA 2008), Sintra, Portugal, Setembro de 2008

alpha-Co(OH)(2)/carbon nanofoam composite as electrochemical capacitor electrode operating at 2 V in aqueous medium

In this work, alpha-Co(OH)(2) is electrodeposited onto carbon nanofoam forming a composite electrode operating in a potential window of 2 V in aqueous medium. Prior to electrodeposition, the carbon nanofoam substrate is subjected to a functionalization process, which leads to an increase of about 40% in its specific capacitance value. Formation of cobalt hydroxide clusters onto the functionalized carbon nanofoam by pulse electrodeposition further enhances the specific capacitance of the electrode. The combination of these factors with an enlarged working potential window, results in a material with specific capacitance close to 300 F g(-1) at current density of 1 A g(-1), considering the total mass loading of the composite. This suggests the potential application of the prepared composites in high energy density electrochemical supercapacitors. (c) 2015 Elsevier B.V. All rights reserved.

Characterisation and electrochemical behaviour of electrodeposited Cu-Fe foams applied as pseudocapacitor electrodes

Copper iron (Cu-Fe) 3D porous foams for supercapacitor electrodes were electrodeposited in the cathodic regime, on stainless steel current collectors, using hydrogen bubbling dynamic template. The foams were prepared at different current densities and deposition times. The foams were submitted to thermal conditioning at temperatures of 150 and 250 degrees C. The morphology, composition and structure of the formed films were studied by SEM, EDS and XRD, respectively. The electrochemical behaviour was studied by cyclic voltammetry, electrochemical impedance spectroscopy and chronopotentiometry. The morphology of the 3D Cu-Fe foams is sensitive to the electrodeposition current and time. The increase of the current density produces a denser, larger and more ramified dendritic structure. Thermal conditioning at high temperature induces a coarser grain structure and the formation of copper oxides, which affect the electrochemical behaviour. The electrochemical response reveals the presence of various redox peaks assigned to the oxidation and reduction of Cu and Fe oxides and hydroxides in the foams. The specific capacitance of the 3D Cu Fe foams was significantly enhanced by thermal conditioning at 150 degrees C. The highest specific capacitance values attained 297 Fg(-1) which are much above the ones typically observed for single Cu or Fe Oxides and hydroxides. These values highlight a synergistic behaviour resulting from the combination of Cu and Fe in the form of nanostructured metallic foams. Moreover, the capacitance retention observed in an 8000 charge/discharge cycling test was above 66%, stating the good performance of these materials and its enhanced electrochemical response as supercapacitor negative electrodes. (C) 2014 Elsevier B.V. All rights reserved.

Electrochemical response of 70Co-30Ni highly branched 3D-dendritic structures for charge storage electrodes

A 70Co-30Ni dendritic alloy was produced on stainless steel by pulse electrodeposition in the cathodic domain, and oxidized by potential cycling. X-ray diffraction (XRD) identified the presence of two phases and scanning electron microscopy (SEM) evidenced an open 3D highly branched dendritic morphology. After potential cycling in 1 M KOH, SEM and X-ray photoelectron spectroscopy (XPS) revealed, respectively, the presence of thin nanoplates, composed of Co and Ni oxi-hydroxides and hydroxides over the original dendritic film. Cyclic voltammetry tests showd the presence of redox peaks assigned to the oxidation and reduction of Ni and Co centres in the surface film. Charge/discharge measurements revealed capacity values of 121 mAh g(1) at 1 mA cm(2). The capacity retention under 8000 cycles was above 70%, stating the good reversibility of these redox materials and its suitability to be used as charge storage electrodes. Electrochemical impedance spectroscopy (EIS) spectra, taken under different applied bias, showed that the capacitance increased when the electrode was fully oxidized and decreased when the electrode was reduced, reflecting different states-of-charge of the electrode. (C) 2015 Elsevier Ltd. All rights reserved.

Simple laccase-based biosensor for formetanate hydrochloride quantification in fruits

This work describes the development of an electrochemical enzymatic biosensor for quantification of the pesticide formetanate hydrochloride (FMT). It is based on a gold electrode modified with electrodeposited gold nanoparticles and laccase. The principle behind its development relies on FMT's capacity to inhibit the laccase catalytic reaction that occurs in the presence of phenolic substrates. The optimum values for the relevant experimental variables such as gold nanoparticles electrochemical deposition (at − 0.2 V for 100 s), laccase immobilization (via glutaraldehyde cross-linking), laccase concentration (12.4 mg/mL), substrate selection and concentration (5.83×10−5 M of aminophenol), pH (5.0), buffer (Britton–Robinson), and square-wave voltammetric parameters were determined. The developed biosensor was successfully applied to FMT determination in mango and grapes. The attained limit of detection was 9.5×10−8 ± 9.5×10−10 M (0.02 ± 2.6×10−4 mg/kg on a fresh fruit weight basis). Recoveries for the five tested spiking levels ranged from 95.5 ± 2.9 (grapes) to 108.6 ± 2.5% (mango). The results indicated that the proposed device presents suitable characteristics in terms of sensitivity (20.58 ± 0.49 A/μM), linearity (9.43×10−7 to 1.13×10−5 M), accuracy, repeatability (RSD of 1.4%), reproducibility (RSD of 1.8%) and stability (19 days) for testing of compliance with established maximum residue limits of FMT in fruits and vegetables.

Electrochemical immunosensor for the analysis of the breast cancer biomarker HER2 ECD

Human epidermal growth factor receptor 2 (HER2) is a breast cancer biomarker that plays a major role in promoting breast cancer cell proliferation and malignant growth. The extracellular domain (ECD) of HER2 can be shed into the blood stream and its concentration is measurable in the serum fraction of blood. In this work an electrochemical immunosensor for the analysis of HER2 ECD in human serum samples was developed. To achieve this goal a screen-printed carbon electrode, modified with gold nanoparticles, was used as transducer surface. A sandwich immunoassay, using two monoclonal antibodies, was employed and the detection of the antibody–antigen interaction was performed through the analysis of an enzymatic reaction product by linear sweep voltammetry. Using the optimized experimental conditions the calibration curve (ip vs. log[HER2 ECD]) was established between 15 and 100 ng/mL and a limit of detection (LOD) of 4.4 ng/mL was achieved. These results indicate that the developed immunosensor could be a promising tool in breast cancer diagnostics, patient follow-up and monitoring of metastatic breast cancer since it allows quantification in a useful concentration range and has an LOD below the established cut-off value (15 ng/mL).