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.

Projeto de um conversor eletrónico para utilização num sistema eólico de produção de energia

Dissertação para obtenção do grau de Mestre em Engenharia Electrotécnica no Ramo de Automação e Electrónica Industrial

A multiplying-by-two CMOS amplifier for high-speed ADCs based on parametric amplification

15th International Conference on Mixed Design of Integrated Circuits and Systems, pp. 177 – 180, Poznan, Polónia

Estudo da turbina de Tesla visando a sua aplicação em sistemas de geração de energia elétrica descentralizada

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

PINPIN a-Si: H based structures for X-ray image detection using the laser scanning technique

Conventional film based X-ray imaging systems are being replaced by their digital equivalents. Different approaches are being followed by considering direct or indirect conversion, with the later technique dominating. The typical, indirect conversion, X-ray panel detector uses a phosphor for X-ray conversion coupled to a large area array of amorphous silicon based optical sensors and a couple of switching thin film transistors (TFT). The pixel information can then be readout by switching the correspondent line and column transistors, routing the signal to an external amplifier. In this work we follow an alternative approach, where the electrical switching performed by the TFT is replaced by optical scanning using a low power laser beam and a sensing/switching PINPIN structure, thus resulting in a simpler device. The optically active device is a PINPIN array, sharing both front and back electrical contacts, deposited over a glass substrate. During X-ray exposure, each sensing side photodiode collects photons generated by the scintillator screen (560 nm), charging its internal capacitance. Subsequently a laser beam (445 nm) scans the switching diodes (back side) retrieving the stored charge in a sequential way, reconstructing the image. In this paper we present recent work on the optoelectronic characterization of the PINPIN structure to be incorporated in the X-ray image sensor. The results from the optoelectronic characterization of the device and the dependence on scanning beam parameters are presented and discussed. Preliminary results of line scans are also presented. (C) 2014 Elsevier B.V. All rights reserved.

Catalytic activity of a benzoyl hydrazone based dimeric dicopper(II) complex in catechol and alcohol oxidation reactions

The benzoyl hydrazone based dimeric dicopper(II) complex [Cu2(R)(CH3O)(NO3)]2(CH3O)2 (R-Cu2+), recently reported by us, catalyzes the aerobic oxidation of catechols (catechol (S1), 3,5- itertiarybutylcatechol (S2) and 3-nitrocatechol (S3)) to the corresponding quinones (catecholase like activity), as shown by UV–Vis absorption spectroscopy in methanol/HEPES buffer (pH 8.2) medium at 25 C. The highest activity is observed for the substituted catechol (S2) with the electron donor tertiary butyl group, resulting in a turnover frequency (TOF) value of 1.13 103 h1. The complex R-Cu2+ also exhibits a good catalytic activity in the oxidation (without added solvent) of 1-phenylethanol to acetophenone by But OOH under low power (10 W) microwave (MW) irradiation. 2014 Elsevier B.V. All rights reserved.

Oxidovanadium complexes with tridentate aroylhydrazone as catalyst precursors for solvent-free microwave-assisted oxidation of alcohols

Aroylhydrazone oxidovanadium compounds, viz, the oxidoethoxidovanadium(V) [VO(OEt)L1] (1) (H2L =salicylaldehyde-2-hydroxybenzoylhydrazone), the salt like dioxidovanadium(V) (NH3CH2CH2OH)(+) [VO2L](-) (2), the mixed-ligand oxidovanadium(V) [VO(hq)L](Hhq = 8-hydroxyquinoline) (3) and the vanadium(IV) [VO(phen)L] (phen=1,10-phenanthroline) (4) complexes (3 and 4 obtained by the first time), have been tested as catalysts for solvent-free microwave-assisted oxidation of aromatic and alicyclic secondary alcohols with tert-butylhydroperoxide. A facile, efficient and selective solvent-free synthesis of ketones was achieved with yields up to 99% (TON= 497, TOF= 993 h(-1) for 3) and 58% (TON =291, TOF= 581 h(-1) for 2) for acetophenone and cyclohexanone, respectively, after 30 min under low power (25W) microwave irradiation. (C) 2015 Elsevier B.V. All rights reserved.

Solvent-free microwave-assisted peroxidative oxidation of alcohols catalyzed by Iron(III)-TEMPO catalytic systems

The iron(III) complexes [H(EtOH)][FeCl2(L)(2)] (1), [H(2)bipy](1/2)[FeCl2(L)(2)].DMF (2) and [FeCl2(L)(2,2'-bipy)] (3) (L = 3-amino-2-pyrazinecarboxylate; H(2)bipy = doubly protonated 4,4'-bipyridine; 2,2'-bipy = 2,2'-bipyridine, DMF = dimethylformamide) have been synthesized and fully characterized by IR, elemental and single-crystal X-ray diffraction analyses, as well as by electrochemical methods. Complexes 1 and 2 have similar mononuclear structures containing different guest molecules (protonated ethanol for 1 and doubly protonated 4,4'-bipyridine for 2) in their lattices, whereas the complex 3 has one 3-amino-2-pyrazinecarboxylate and a 2,2'-bipyridine ligand. They show a high catalytic activity for the low power (10 W) solvent-free microwave assisted peroxidative oxidation of 1-phenylethanol, leading, in the presence of TEMPO, to quantitative yields of acetophenone [TOFs up to 8.1 x 10(3) h(-1), (3)] after 1 h. Moreover, the catalysts are of easy recovery and reused, at least for four consecutive cycles, maintaining 83 % of the initial activity and concomitant rather high selectivity. 3-Amino-2-pyrazinecarboxylic acid is used to synthesize three new iron(III) complexes which act as heterogeneous catalysts for the solvent-free microwave-assisted peroxidative oxidation of 1-phenylethanol.

A survey of wireless technologies coexistence in WBAN: analysis and open research issues

Wireless Body Area Network (WBAN) is the most convenient, cost-effective, accurate, and non-invasive technology for e-health monitoring. The performance of WBAN may be disturbed when coexisting with other wireless networks. Accordingly, this paper provides a comprehensive study and in-depth analysis of coexistence issues and interference mitigation solutions in WBAN technologies. A thorough survey of state-of-the art research in WBAN coexistence issues is conducted. The survey classified, discussed, and compared the studies according to the parameters used to analyze the coexistence problem. Solutions suggested by the studies are then classified according to the followed techniques and concomitant shortcomings are identified. Moreover, the coexistence problem in WBAN technologies is mathematically analyzed and formulas are derived for the probability of successful channel access for different wireless technologies with the coexistence of an interfering network. Finally, extensive simulations are conducted using OPNET with several real-life scenarios to evaluate the impact of coexistence interference on different WBAN technologies. In particular, three main WBAN wireless technologies are considered: IEEE 802.15.6, IEEE 802.15.4, and low-power WiFi. The mathematical analysis and the simulation results are discussed and the impact of interfering network on the different wireless technologies is compared and analyzed. The results show that an interfering network (e.g., standard WiFi) has an impact on the performance of WBAN and may disrupt its operation. In addition, using low-power WiFi for WBANs is investigated and proved to be a feasible option compared to other wireless technologies.

Localization system for pedestrians based on sensor and information fusion

Nowadays there is an increase of location-aware mobile applications. However, these applications only retrieve location with a mobile device's GPS chip. This means that in indoor or in more dense environments these applications don't work properly. To provide location information everywhere a pedestrian Inertial Navigation System (INS) is typically used, but these systems can have a large estimation error since, in order to turn the system wearable, they use low-cost and low-power sensors. In this work a pedestrian INS is proposed, where force sensors were included to combine with the accelerometer data in order to have a better detection of the stance phase of the human gait cycle, which leads to improvements in location estimation. Besides sensor fusion an information fusion architecture is proposed, based on the information from GPS and several inertial units placed on the pedestrian body, that will be used to learn the pedestrian gait behavior to correct, in real-time, the inertial sensors errors, thus improving location estimation.

Autoconsumo fotovoltaico, um elemento de eficiência energética. Caso de estudo: ISEP

Mestrado em Energias Sustentáveis

Sulfonated Schiff base copper(ii) complexes as efficient and selective catalysts in alcohol oxidation: syntheses and crystal structures

The reaction between 2-aminobenzenesulfonic acid and 2-hydroxy-3-methoxybenzaldehyde produces the acyclic Schiff base 2-[(2-hydroxy-3-methoxyphenyl) methylideneamino] benzenesulfonic acid (H2L center dot 3H(2)O) (1). In situ reactions of this compound with Cu(II) salts and, eventually, in the presence of pyridine (py) or 2,2'-bipyridine (2,2'-bipy) lead to the formation of the mononuclear complexes [CuL(H2O)(2)] (2) and [CuL(2,2'-bipy)]center dot DMF center dot H2O (3) and the diphenoxo-bridged dicopper compounds [CuL(py)](2) (4) and [CuL(EtOH)](2)center dot 2H(2)O (5). In 2-5 the L-2-ligand acts as a tridentate chelating species by means of one of the O-sulfonate atoms, the O-phenoxo and the N-atoms. The remaining coordination sites are then occupied by H2O (in 2), 2,2'-bipyridine (in 3), pyridine (in 4) or EtOH (in 5). Hydrogen bond interactions resulted in R-2(2) (14) and in R-4(4)(12) graph sets leading to dimeric species (in 2 and 3, respectively), 1D chain associations (in 2 and 5) or a 2D network (1). Complexes 2-5 are applied as selective catalysts for the homogeneous peroxidative (with tert-butylhydroperoxide, TBHP) oxidation of primary and secondary alcohols, under solvent-and additive-free conditions and under low power microwave (MW) irradiation. A quantitative yield of acetophenone was obtained by oxidation of 1-phenylethanol with compound 4 [TOFs up to 7.6 x 10(3) h(-1)] after 20 min of MW irradiation, whereas the oxidation of benzyl alcohol to benzaldehyde is less effective (TOF 992 h(-1)). The selectivity of 4 to oxidize the alcohol relative to the ene function is demonstrated when using cinnamyl alcohol as substrate.

Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols

A one-pot template reaction of sodium 2-(2-(dicyanomethylene) hydrazinyl) benzenesulfonate (NaHL1) with water and manganese(II) acetate tetrahydrate led to the mononuclear complex [Mn(H2O)(6)](HL1a)(2)center dot 4H(2)O (1), where (HL1a) -= 2-(SO3-)C6H4(NH)=N=C(C N) (CONH2) is the carboxamide species derived from nucleophilic attack of water on a cyano group of (HL1) . The copper tetramer [Cu-4(H2O)(10)(-) (1 kappa N: kappa O-2: kappa O, 2 kappa N: k(O)-L-2)(2)]center dot 2H(2)O (2) was obtained from reaction of Cu(NO3)(2)center dot 2.5H(2)O with sodium 5-(2( 4,4-dimethyl-2,6-dioxocyclohexylidene) hydrazinyl)-4-hydroxybenzene-1,3-disulfonate (Na2H2L2). Both complexes were characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. They exhibit a high catalytic activity for the solvent-and additive-free microwave (MW) assisted oxidation of primary and secondary alcohols with tert-butylhydroperoxide, leading to yields of the oxidized products up to 85.5% and TOFs up to 1.90 x 103 h(-1) after 1 h under low power (5-10 W) MW irradiation. Moreover, the heterogeneous catalysts are easily recovered and reused, at least for three consecutive cycles, maintaining 89% of the initial activity and a high selectivity.

Oriented Tailoring of Plastic Antibodies for Prostate Specific Antigen and Application of the Imprinted Material as Ionophore in Potentiometric Detection

Prostate Specific Antigen (PSA) is the biomarker of choice for screening prostate cancer throughout the population, with PSA values above 10 ng/mL pointing out a high probability of associated cancer1. According to the most recent World Health Organization (WHO) data, prostate cancer is the commonest form of cancer in men in Europe2. Early detection of prostate cancer is thus very important and is currently made by screening PSA in men over 45 years old, combined with other alterations in serum and urine parameters. PSA is a glycoprotein with a molecular mass of approximately 32 kDa consisting of one polypeptide chain, which is produced by the secretory epithelium of human prostate. Currently, the standard methods available for PSA screening are immunoassays like Enzyme-Linked Immunoabsorbent Assay (ELISA). These methods are highly sensitive and specific for the detection of PSA, but they require expensive laboratory facilities and high qualify personal resources. Other highly sensitive and specific methods for the detection of PSA have also become available and are in its majority immunobiosensors1,3-5, relying on antibodies. Less expensive methods producing quicker responses are thus needed, which may be achieved by synthesizing artificial antibodies by means of molecular imprinting techniques. These should also be coupled to simple and low cost devices, such as those of the potentiometric kind, one approach that has been proven successful6. Potentiometric sensors offer the advantage of selectivity and portability for use in point-of-care and have been widely recognized as potential analytical tools in this field. The inherent method is simple, precise, accurate and inexpensive regarding reagent consumption and equipment involved. Thus, this work proposes a new plastic antibody for PSA, designed over the surface of graphene layers extracted from graphite. Charged monomers were used to enable an oriented tailoring of the PSA rebinding sites. Uncharged monomers were used as control. These materials were used as ionophores in conventional solid-contact graphite electrodes. The obtained results showed that the imprinted materials displayed a selective response to PSA. The electrodes with charged monomers showed a more stable and sensitive response, with an average slope of -44.2 mV/decade and a detection limit of 5.8X10-11 mol/L (2 ng/mL). The corresponding non-imprinted sensors showed smaller sensitivity, with average slopes of -24.8 mV/decade. The best sensors were successfully applied to the analysis of serum samples, with percentage recoveries of 106.5% and relatives errors of 6.5%.

Energy Harvesting for Autonomous Underwater Vehicles

In this study, energy production for autonomous underwater vehicles is investigated. This project is part of a bigger project called TURTLE. The autonomous vehicles perform oceanic researches at seabed for which they are intended to be kept operational underwater for several months. In order to ful l a long-term underwater condition, powerful batteries are combined with \micro- scale" energy production on the spot. This work tends to develop a system that generates power up to a maximum of 30 W. Latter energy harvesting structure consists basically of a turbine combined with a generator and low-power electronics to adjust the achieved voltage to a required battery charger voltage. Every component is examined separately hence an optimum can be de ned for all, and subsequently also an overall optimum. Di erent design parameters as e.g. number of blades, solidity ratio and cross-section area are compared for di erent turbines, in order to see what is the most feasible type. Further, a generator is chosen by studying how ux distributions might be adjusted to low velocities, and how cogging torque can be excluded by adapted designs. Low-power electronics are con gured in order to convert and stabilize heavily varying three-phase voltages to a constant, recti ed voltage which is usable for battery storage. Clearly, di erent component parameters as maximum power and torque are matched here to increase the overall power generation. Furthermore an overall maximum power is set up for achieving a maximum power ow at load side. Due to among others typical low velocities of about 0.1 to 0.5 m/s, and constructing limits of the prototype, the vast range of components is restricted to only a few that could be used. Hence, a helical turbine is combined in a direct drive mode to a coreless-stator axial- ux permanent-magnet generator, from which the output voltage is adjusted subsequently by a recti er, impedance matching unit, upconverter circuit and an overall control unit to regulate di erent component parameters. All these electronics are combined in a closed-loop design to involve positive feedback signals. Furthermore a theoretical con guration for the TURTLE vehicle is described in this work and a solution is proposed that might be implemented, for which several design tests are performable in a future study.