Dinuclear Mn (II,II) complexes: magnetic properties and microwave assisted oxidation of alcohols

A series of six new mixed-ligand dinuclear Mn(II, II) complexes of three different hydrazone Schiff bases (H3L1, H3L2 and H3L3), derived from condensation of the aromatic acid hydrazides benzohydrazide, 2-aminobenzohydrazide or 2-hydroxybenzohydrazide, with 2,3-dihydroxy benzaldehyde, respectively, is reported. Reactions of Mn(NO3)(2) center dot 4H(2)O with the H3L1-3 compounds, in the presence of pyridine (1 : 1 : 1 mole ratio), in methanol at room temperature, yield [Mn(H2L1)(py)(H2O)](2)(NO3)(2) center dot 2H(2)O (1 center dot 2H(2)O), [Mn(H2L2)(py)(CH3OH)](2)(NO3)(2) center dot 4H(2)O (2 center dot 4H(2)O) and [Mn(H2L3)(py)(H2O)](2)(NO3)(2) (3) respectively, whereas the use of excess pyridine yields complexes with two axially coordinated pyridine molecules at each Mn(II) centre, viz. [Mn(H2L1)(py)(2)] 2(NO3)(2) center dot H2O (4 center dot H2O), [Mn(H2L2)(py) H-O (6 center dot 2CH(3)OH), respectively. In all the complexes, the (H2L1-3)-ligand coordinates in the keto form. Complexes 1 center dot 2H(2)O, 2 center dot 4H(2)O, 4 center dot H2O, 5 center dot 2H(2)O and 6 center dot 2CH(3)OH are characterized by single crystal X-ray diffraction analysis. The complexes 1, 2 and 6, having different coordination environments, have been selected for variable temperature magnetic susceptibility measurements to examine the nature of magnetic interaction between magnetically coupled Mn(II) centres and also for exploration of the catalytic activity towards microwave assisted oxidation of alcohols. A yield of 81% (acetophenone) is obtained using a maximum of 0.4% molar ratio of catalyst relative to the substrate in the presence of TEMPO and in aqueous basic solution, under mild conditions.

Microwave-assisted and solvent-free peroxidative oxidation of 1-phenylethanol to acetophenone with a CuII-TEMPO catalytic system

The water-soluble copper(II) complex [Cu(H2R)(HL)]center dot H2O (1) was prepared by reaction of copper(II) nitrate hydrate with (E)-2-(((1-hydroxynaphthalen-2-yl)methylene)amino) benzenesulfonic acid (H2L) and diethanolamine (H3R). It was characterized by IR and ESI-MS spectroscopies, elemental and X-ray crystal structural analyses. 1 shows a high catalytic activity for the solvent-free microwave (MW) assisted oxidation of 1-phenylethanol with tert-butylhydroperoxide, leading, in the presence of TEMPO, to yields up to 85% (TON = 850) in a remarkably short reaction time (15 min, with the corresponding TOE value of 3.40 x 10(3) h(-1)) under low power (25W) MW irradiation. Crown Copyright (C) 2014 Published by Elsevier B.V. All rights reserved.

Design and optimization of na ultra wideband and compact microwave antenna for radiometric monitoring of brain temperature

We present the modeling efforts on antenna design and frequency selection to monitor brain temperature during prolonged surgery using noninvasive microwave radiometry. A tapered log-spiral antenna design is chosen for its wideband characteristics that allow higher power collection from deep brain. Parametric analysis with the software HFSS is used to optimize antenna performance for deep brain temperature sensing. Radiometric antenna efficiency (eta) is evaluated in terms of the ratio of power collected from brain to total power received by the antenna. Anatomical information extracted from several adult computed tomography scans is used to establish design parameters for constructing an accurate layered 3-D tissue phantom. This head phantom includes separate brain and scalp regions, with tissue equivalent liquids circulating at independent temperatures on either side of an intact skull. The optimized frequency band is 1.1-1.6 GHz producing an average antenna efficiency of 50.3% from a two turn log-spiral antenna. The entire sensor package is contained in a lightweight and low-profile 2.8 cm diameter by 1.5 cm high assembly that can be held in place over the skin with an electromagnetic interference shielding adhesive patch. The calculated radiometric equivalent brain temperature tracks within 0.4 degrees C of the measured brain phantom temperature when the brain phantom is lowered 10. C and then returned to the original temperature (37 degrees C) over a 4.6-h experiment. The numerical and experimental results demonstrate that the optimized 2.5-cm log-spiral antenna is well suited for the noninvasive radiometric sensing of deep brain temperature.

Automated design of microwave discrete tuning differential capacitance circuits in Si-integrated technologies

A genetic algorithm used to design radio-frequency binary-weighted differential switched capacitor arrays (RFDSCAs) is presented in this article. The algorithm provides a set of circuits all having the same maximum performance. This article also describes the design, implementation, and measurements results of a 0.25 lm BiCMOS 3-bit RFDSCA. The experimental results show that the circuit presents the expected performance up to 40 GHz. The similarity between the evolutionary solutions, circuit simulations, and measured results indicates that the genetic synthesis method is a very useful tool for designing optimum performance RFDSCAs.

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.

Numerical 3D modeling of heat transfer in human tissues for microwave radiometry monitoring of Brown fat metabolismo

Background: Brown adipose tissue (BAT) plays an important role in whole body metabolism and could potentially mediate weight gain and insulin sensitivity. Although some imaging techniques allow BAT detection, there are currently no viable methods for continuous acquisition of BAT energy expenditure. We present a non-invasive technique for long term monitoring of BAT metabolism using microwave radiometry. Methods: A multilayer 3D computational model was created in HFSS™ with 1.5 mm skin, 3-10 mm subcutaneous fat, 200 mm muscle and a BAT region (2-6 cm3) located between fat and muscle. Based on this model, a log-spiral antenna was designed and optimized to maximize reception of thermal emissions from the target (BAT). The power absorption patterns calculated in HFSS™ were combined with simulated thermal distributions computed in COMSOL® to predict radiometric signal measured from an ultra-low-noise microwave radiometer. The power received by the antenna was characterized as a function of different levels of BAT metabolism under cold and noradrenergic stimulation. Results: The optimized frequency band was 1.5-2.2 GHz, with averaged antenna efficiency of 19%. The simulated power received by the radiometric antenna increased 2-9 mdBm (noradrenergic stimulus) and 4-15 mdBm (cold stimulus) corresponding to increased 15-fold BAT metabolism. Conclusions: Results demonstrated the ability to detect thermal radiation from small volumes (2-6 cm3) of BAT located up to 12 mm deep and to monitor small changes (0.5°C) in BAT metabolism. As such, the developed miniature radiometric antenna sensor appears suitable for non-invasive long term monitoring of BAT metabolism.

The contribution of multitemporal information from multispectral satellite images for automatic land cover classification at the national scale

Thesis submitted to the Instituto Superior de Estatística e Gestão de Informação da Universidade Nova de Lisboa in partial fulfillment of the requirements for the Degree of Doctor of Philosophy in Information Management – Geographic Information Systems

Passive haemagglutination test for human neurocysticercosis immunodiagnosis: I. Standardization and evaluation of the passive haemagglutination test for the detection of anti-Cysticercus cellulosae antibodies

A passive haemagglutination test (PHA) for human neurocysticercosis was standardized and evaluated for the detection of specific antibodies to Cysticercus cellulosae in cerebrospinal fluid (CSF). For the assay, formaldehyde-treated group O Rh-human red cells coated with the cysticerci crude total saline extract (TS) antigen were employed. A total of 115 CSF samples from patients with neurocysticercosis was analysed, of these 94 presented reactivity, corresponding to 81.7% sensitivity, in which confidence limit of 95% probability (CL95%) ranged from 74.5% to 88.9%. Eighty-nine CSF samples derived from individuals of control group presented as nonreactive in 94.4% (CL95% from 89.6% to 99.2%). The positive and negative predictive values were 1.4% and 99.9%, respectively, considering the mean rate of that this assay provide a rapid, highly reproducible, and moderately sensitive mean of detecting specific antibodies in CSF samples.

Passive haemagglutination test for human neurocysticercosis immunodiagnosis: II - Comparison of two standardized procedures for the passive haemagglutination reagent in the detection of anti-Cysticercus cellulosae antibodies in cerebrospinal fluids

A comparison of two different standardized reagent procedures for the passive haemagglutination test (PHA) in the detection of specific antibody to Cysticercus cellulosae in cerebrospinal fluid (CSF) was carried out. The formaldehyde-treated group O Rh-human red blood cells (HuRBC) and glutaraldehyde-treated sheep red blood cells (SRBC) were the supplies for the reagents preparation and, in the tests, they were designated as PHA-1 and PHA-2, respectively. For both reagents the cells were coated with the cysticerci total saline extract (TS) antigen. PHA-1 and PHA-2 were assessed in a total of 204 CSF from patients with neurocysticercosis, from non-related infections and from healthy individuals. The positivity and specificity indices obtained were respectively 81.7% and 94.4% for PHA-1 and for PHA-2, 88.7% and 96.6%. Since no significant differences were observed between the results provided by two reagents, at level of significance of 0.05, either processes of cell sensitization can alternatively be used according to the own laboratory convenience.

Télédetection en milieu périurbain. Détection et localisation du changement de l'occupation du sol par intégration des donnés-satellite SPOT HRV dans un système d'information géographique

Thèse pour obtenir le grade de DOCTEUR DE L' UNIVERSITÉ PARIS XII, Discipline: Urbanisme Aménagement

Design of New Materials for Passive Vibration Control

The objective of this contribution is to extend the models of cellular/composite material design to nonlinear material behaviour and apply them for design of materials for passive vibration control. As a first step a computational tool allowing determination of optimised one-dimensional isolator behaviour was developed. This model can serve as a representation for idealised macroscopic behaviour. Optimal isolator behaviour to a given set of loads is obtained by generic probabilistic metaalgorithm, simulated annealing. Cost functional involves minimization of maximum response amplitude in a set of predefined time intervals and maximization of total energy absorbed in the first loop. Dependence of the global optimum on several combinations of leading parameters of the simulated annealing procedure, like neighbourhood definition and annealing schedule, is also studied and analyzed. Obtained results facilitate the design of elastomeric cellular materials with improved behaviour in terms of dynamic stiffness for passive vibration control.

Deep crustal structure across a young passive margin from wide-angle and reflection seismic data (The Sardinia Experiment) - I. Gulf of Lion's margin

The conjugate margins system of the Gulf of Lion and West Sardinia (GLWS) represents a unique natural laboratory for addressing fundamental questions about rifting due to its landlocked situation, its youth, its thick sedimentary layers, including prominent palaeo-marker such as the MSC event, and the amount of available data and multidisciplinary studies. The main goals of the SARDINIA experiment, were to (i) investigate the deep structure of the entire system within the two conjugate margins: the Gulf of Lion and West Sardinia, (ii) characterize the nature of the crust, and (iii) define the geometry of the basin and provide important constrains on its genesis. This paper presents the results of P-wave velocity modelling on three coincident near-vertical reflection multi-channel seismic (MCS) and wide-angle seismic profiles acquired in the Gulf of Lion, to a depth of 35 km. A companion paper [part II Afilhado et al., 2015] addresses the results of two other SARDINIA profiles located on the oriental conjugate West Sardinian margin. Forward wide-angle modelling of both data sets confirms that the margin is characterised by three distinct domains following the onshore unthinned, 33 km-thick continental crust domain: Domain I is bounded by two necking zones, where the crust thins respectively from 30 to 20 and from 20 to 7 km over a width of about 170 km; the outermost necking is imprinted by the well-known T-reflector at its crustal base; Domain II is characterised by a 7 km-thick crust with anomalous velocities ranging from 6 to 7.5 km/s; it represents the transition between the thinned continental crust (Domain I) and a very thin (only 4-5 km) "atypical" oceanic crust (Domain III). In Domain II, the hypothesis of the presence of exhumed mantle is falsified by our results: this domain may likely consist of a thin exhumed lower continental crust overlying a heterogeneous, intruded lower layer. Moreover, despite the difference in their magnetic signatures, Domains II and III present the very similar seismic velocities profiles, and we discuss the possibility of a connection between these two different domains.

Deep crustal structure across a young passive margin from wide-angle and reflection seismic data (The Sardinia Experiment) - II. Sardinia's margin

Geophysical data acquired on the conjugate margins system of the Gulf of Lion and West Sardinia (GLWS) is unique in its ability to address fundamental questions about rifting (i.e. crustal thinning, the nature of the continent-ocean transition zone, the style of rifting and subsequent evolution, and the connection between deep and surface processes). While the Gulf of Lion (GoL) was the site of several deep seismic experiments, which occurred before the SARDINIA Experiment (ESP and ECORS Experiments in 1981 and 1988 respectively), the crustal structure of the West Sardinia margin remains unknown. This paper describes the first modeling of wide-angle and near-vertical reflection multi-channel seismic (MCS) profiles crossing the West Sardinia margin, in the Mediterranean Sea. The profiles were acquired, together with the exact conjugate of the profiles crossing the GoL, during the SARDINIA experiment in December 2006 with the French R/V L'Atalante. Forward wide-angle modeling of both data sets (wide-angle and multi-channel seismic) confirms that the margin is characterized by three distinct domains following the onshore unthinned, 26 km-thick continental crust : Domain V, where the crust thins from 26 to 6 km in a width of about 75 km; Domain IV where the basement is characterized by high velocity gradients and lower crustal seismic velocities from 6.8 to 7.25 km/s, which are atypical for either crustal or upper mantle material, and Domain III composed of "atypical" oceanic crust.The structure observed on the West Sardinian margin presents a distribution of seismic velocities that is symmetrical with those observed on the Gulf of Lion's side, except for the dimension of each domain and with respect to the initiation of seafloor spreading. This result does not support the hypothesis of simple shear mechanism operating along a lithospheric detachment during the formation of the Liguro-Provencal basin.

RFID-based wireless passive sensors utilizing cork materials

This paper presents the design of low-cost, conformal UHF antennas and RFID tags on two types of cork substrates: 1) natural cork and 2) agglomerate cork. Such RFID tags find an application in wine bottle and barrel identification, and in addition, they are suitable for numerous antenna-based sensing applications. This paper includes the high-frequency characterization of the selected cork substrates considering the anisotropic behavior of such materials. In addition, the variation of their permittivity values as a function of the humidity is also verified. As a proof-of-concept demonstration, three conformal RFID tags have been implemented on cork, and their performance has been evaluated using both a commercial Alien ALR8800 reader and an in-house measurement setup. The reading of all tags has been checked, and a satisfactory performance has been verified, with reading ranges spanning from 0.3 to 6 m. In addition, this paper discusses how inkjet printing can be applied to cork surfaces, and an RFID tag printed on cork is used as a humidity sensor. Its performance is tested under different humidity conditions, and a good range in excess of 3 m has been achieved, allied to a good sensitivity obtained with a shift of >5 dB in threshold power of the tag for different humid conditions.

Multi-elemental analysis of ready-to-eat “baby leaf” vegetables using microwave digestion and high-resolution continuum source atomic absorption spectrometry

The mineral content (phosphorous (P), potassium (K), sodium (Na), calcium (Ca), magnesium (Mg), iron (Fe), manganese (Mn), zinc (Zn) and copper (Cu)) of eight ready-to-eat baby leaf vegetables was determined. The samples were subjected to microwave-assisted digestion and the minerals were quantified by High-Resolution Continuum Source Atomic Absorption Spectrometry (HR-CS-AAS) with flame and electrothermal atomisation. The methods were optimised and validated producing low LOQs, good repeatability and linearity, and recoveries, ranging from 91% to 110% for the minerals analysed. Phosphorous was determined by a standard colorimetric method. The accuracy of the method was checked by analysing a certified reference material; results were in agreement with the quantified value. The samples had a high content of potassium and calcium, but the principal mineral was iron. The mineral content was stable during storage and baby leaf vegetables could represent a good source of minerals in a balanced diet. A linear discriminant analysis was performed to compare the mineral profile obtained and showed, as expected, that the mineral content was similar between samples from the same family. The Linear Discriminant Analysis was able to discriminate different samples based on their mineral profile.