Inherently chiral calix[4]arenes with planar chirality: two new entries to the family

The synthesis of two new inherently chiral calix[4]arenes (ICCs, 1 and 2), endowed with electron-rich concave surfaces, has been achieved through the desymmetrization of a lower rim distal-bridged oxacyclophane (OCP) macrocycle. The new highly emissive ICCs were resolved by chiral HPLC, and the enantiomeric nature of the isolated antipodes proved by electronic circular dichroism (CD). Using time-dependent density functional calculations of CD spectra, their absolute configurations were established. NMR studies with (S)-Pirkle's alcohol unequivocally showed that the host-guest interactions occur in the chiral pocket comprehending the calix-OCP exo cavities and the carbazole moieties.

Budget impact from the incorporation of positron emission tomography – computed tomography for staging lung cancers

OBJECTIVE To estimate the budget impact from the incorporation of positron emission tomography (PET) in mediastinal and distant staging of non-small cell lung cancer.METHODS The estimates were calculated by the epidemiological method for years 2014 to 2018. Nation-wide data were used about the incidence; data on distribution of the disease´s prevalence and on the technologies’ accuracy were from the literature; data regarding involved costs were taken from a micro-costing study and from Brazilian Unified Health System (SUS) database. Two strategies for using PET were analyzed: the offer to all newly-diagnosed patients, and the restricted offer to the ones who had negative results in previous computed tomography (CT) exams. Univariate and extreme scenarios sensitivity analyses were conducted to evaluate the influence from sources of uncertainties in the parameters used.RESULTS The incorporation of PET-CT in SUS would imply the need for additional resources of 158.1 BRL (98.2 USD) million for the restricted offer and 202.7 BRL (125.9 USD) million for the inclusive offer in five years, with a difference of 44.6 BRL (27.7 USD) million between the two offer strategies within that period. In absolute terms, the total budget impact from its incorporation in SUS, in five years, would be 555 BRL (345 USD) and 600 BRL (372.8 USD) million, respectively. The costs from the PET-CT procedure were the most influential parameter in the results. In the most optimistic scenario, the additional budget impact would be reduced to 86.9 BRL (54 USD) and 103.8 BRL (64.5 USD) million, considering PET-CT for negative CT and PET-CT for all, respectively.CONCLUSIONS The incorporation of PET in the clinical staging of non-small cell lung cancer seems to be financially feasible considering the high budget of the Brazilian Ministry of Health. The potential reduction in the number of unnecessary surgeries may cause the available resources to be more efficiently allocated.

Calix[4]arene-carbazole-containing polymers: synthesis and properties

New highly fluorescent calix[4]arene-containing phenylene-alt-ethynylene-3,6- and 2,7-carbazolylene polymers (CALIX-PPE-CBZs) have been synthesized for the first time and their photophysical properties evaluated. Both polymers were obtained in good isolated yields (70-84%), having M-w ranging from 7660-26,700 g mol(-1). It was found that the diethynyl substitution (3,6- or 2,7-) pattern on the carbazole monomers markedly influences the degree of polymerization. The amorphous yellow polymers are freely soluble in several nonprotic organic solvents and have excellent film forming abilities. TG/DSC analysis evidences similar thermal behaviors for both polymers despite their quite different molecular weight distributions and main-chain connectivities (T-g, in the range 83-95 degrees C and decomposition onsets around 270 degrees C). The different conjugation lengths attained by the two polymers dictates much of their photophysical properties. Thus, whereas the fully conjugated CALIX-PPE-2,7-CBZ has its emission maximum at 430 nm (E-g = 2.84 eV; Phi(F) = 0.62, CHCl3), the 3,6-linked counterpart (CALIX-PPE-3,6-CBZ) fluoresces at 403 nm with a significant lower quantum yield (E-g = 3.06 eV; Phi(F) = 0.31, CHCl3). The optical properties of both polymers are predominantly governed by the intrachain electronic properties of the conjugated backbones owing to the presence of calix[4]arenes along the polymer chain which disfavor significant interchain interactions, either in fluid- or solid-state.

Robotic manipulators with vibrations: short time fourier transform of fractional spectra

This paper analyzes the signals captured during impacts and vibrations of a mechanical manipulator. In order to acquire and study the signals an experimental setup is implemented. The signals are treated through signal processing tools such as the fast Fourier transform and the short time Fourier transform. The results show that the Fourier spectrum of several signals presents a non integer behavior. The experimental study provides valuable results that can assist in the design of a control system to deal with the unwanted effects of vibrations.

Production and decay of Sulphur excited species in a ECRIS plasma

The most important processes for the creation of S12+ to S14+ ions excited states from the ground configurations of S9+ to S14+ ions in an electron cyclotron resonance ion source, leading to the emission of K X-ray lines, are studied. Theoretical values for inner-shell excitation and ionization cross sections, including double KL and triple KLL ionization, transition probabilities and energies for the deexcitation processes, are calculated in the framework of the multi-configuration Dirac-Fock method. With reasonable assumptions about the electron energy distribution, a theoretical K$\alpha$ X-ray spectrum is obtained, which is compared to recent experimental data.

Implementation of a new reference values database for semiquantification in123I-FP-CIT brain single emission tomography

Brain dopamine transporters imaging by Single Emission Tomography (SPECT) with 123I-FP-CIT (DaTScanTM) has become an important tool in the diagnosis and evaluation of Parkinson syndromes.This diagnostic method allows the visualization of a portion of the striatum – where healthy pattern resemble two symmetric commas - allowing the evaluation of dopamine presynaptic system, in which dopamine transporters are responsible for dopamine release into the synaptic cleft, and their reabsorption into the nigrostriatal nerve terminals, in order to be stored or degraded. In daily practice for assessment of DaTScan TM, it is common to rely only on visual assessment for diagnosis. However, this process is complex and subjective as it depends on the observer’s experience and it is associated with high variability intra and inter observer. Studies have shown that semiquantification can improve the diagnosis of Parkinson syndromes. For semiquantification, analysis methods of image segmentation using regions of interest (ROI) are necessary. ROIs are drawn, in specific - striatum - and in nonspecific – background – uptake areas. Subsequently, specific binding ratios are calculated. Low adherence of semiquantification for diagnosis of Parkinson syndromes is related, not only with the associated time spent, but also with the need of an adapted database of reference values for the population concerned, as well as, the examination of each service protocol. Studies have concluded, that this process increases the reproducibility of semiquantification. The aim of this investigation was to create and validate a database of healthy controls for Dopamine transporters with DaTScanTM named DBRV. The created database has been adapted to the Nuclear Medicine Department’s protocol, and the population of Infanta Cristina’s Hospital located in Badajoz, Spain.

Métodos "verdes" de produção de nanomateriais que promovem nanotecnologias sustentáveis

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

Assessment of heavy metals in the surroundings of coal-fired power plant

This paper aims to survey metal concentrations in soils in the vicinity of a coal-firedpower plant located in southwest of Portugal. Two annual sampling campaigns were carried out to measure a hypothetical soil contamination around the coal plant. The sampling area was divided into two subareas, both centered in the emission source, delimited by two concentric circles with radius of 6 km and 20 km. About 40 samplings points were defined in the influence area. Metals measurements were performed with a portable analytical X-ray dispersive energy fluorescence spectrometer identifying about 20 different elements in each sampling point. The most relevant elements measured included As, Cu, Fe, Hg, Pb, Ti and Zn in both sampling areas. Considering the results obtained in the first sampling campaign, arsenic is predominantly higher within the 6-20 km sampling area. The second sampling campaign showed that both sampling areas presented relatively similar metal concentrations except for Fe, Mn, Sr and Zn which concentration is higher within the 6-20 km sampling area. Also, As, Fe, Mn and Ti concentrations decreased significantly from the first to the second sampling campaign and their concentration were predominately higher in the NE-E and E-SE directions.

Self-scheduling and bidding strategies of thermal units with stochastic emission constraints

This paper is on the self-scheduling problem for a thermal power producer taking part in a pool-based electricity market as a price-taker, having bilateral contracts and emission-constrained. An approach based on stochastic mixed-integer linear programming approach is proposed for solving the self-scheduling problem. Uncertainty regarding electricity price is considered through a set of scenarios computed by simulation and scenario-reduction. Thermal units are modelled by variable costs, start-up costs and technical operating constraints, such as: forbidden operating zones, ramp up/down limits and minimum up/down time limits. A requirement on emission allowances to mitigate carbon footprint is modelled by a stochastic constraint. Supply functions for different emission allowance levels are accessed in order to establish the optimal bidding strategy. A case study is presented to illustrate the usefulness and the proficiency of the proposed approach in supporting biding strategies. (C) 2014 Elsevier Ltd. All rights reserved.

On similarities in infrared spectra of complex drugs

A chromatographic separation of active ingredients of Combivir, Epivir, Kaletra, Norvir, Prezista, Retrovir, Trivizir, Valcyte, and Viramune is performed on thin layer chromatography. The spectra of these nine drugs were recorded using the Fourier transform infrared spectroscopy. This information is then analyzed by means of the cosine correlation. The comparison of the infrared spectra in the perspective of the adopted similarity measure is possible to visualize with present day computer tools, and the emerging clusters provide additional information about the similarities of the investigated set of complex drugs.

Fast unsupervised technique for extraction of endmembers spectra from hyperspectral data

One of the most challenging task underlying many hyperspectral imagery applications is the linear unmixing. The key to linear unmixing is to find the set of reference substances, also called endmembers, that are representative of a given scene. This paper presents the vertex component analysis (VCA) a new method to unmix linear mixtures of hyperspectral sources. The algorithm is unsupervised and exploits a simple geometric fact: endmembers are vertices of a simplex. The algorithm complexity, measured in floating points operations, is O (n), where n is the sample size. The effectiveness of the proposed scheme is illustrated using simulated data.

Energy-dispersive x-ray fluorescence analysis of modern coloured glasses from Marinha Grande (Portugal)

X-Ray Spectrom. 2003; 32: 396–401

Glass in Cultural Heritage – An Introduction

Proceedings of the Chemistry and Conservation Science

Fast unsupervised extraction of endmembers spectra from hyperspectral data

Linear unmixing decomposes an hyperspectral image into a collection of re ectance spectra, called endmember signatures, and a set corresponding abundance fractions from the respective spatial coverage. This paper introduces vertex component analysis, an unsupervised algorithm to unmix linear mixtures of hyperpsectral data. VCA exploits the fact that endmembers occupy vertices of a simplex, and assumes the presence of pure pixels in data. VCA performance is illustrated using simulated and real data. VCA competes with state-of-the-art methods with much lower computational complexity.

Use of a fluorescence-based approach to assess short-term responses of the alga Pseudokirchneriella subcapitata to metal stress

This work explores the use of fluorescent probes to evaluate the responses of the green alga Pseudokirchneriella subcapitata to the action of three nominal concentrations of Cd(II), Cr(VI), Cu(II) and Zn(II) for a short time (6 h). The toxic effect of the metals on algal cells was monitored using the fluorochromes SYTOX Green (SG, membrane integrity), fluorescein diacetate (FDA, esterase activity) and rhodamine 123 (Rh123, mitochondrial membrane potential). The impact of metals on chlorophyll a (Chl a) autofluorescence was also evaluated. Esterase activity was the most sensitive parameter. At the concentrations studied, all metals induced the loss of esterase activity. SG could be used to effectively detect the loss of membrane integrity in algal cells exposed to 0.32 or 1.3 μmol L−1 Cu(II). Rh123 revealed a decrease in the mitochondrial membrane potential of algal cells exposed to 0.32 and 1.3 μmol L−1 Cu(II), indicating that mitochondrial activity was compromised. Chl a autofluorescence was also affected by the presence of Cr(VI) and Cu(II), suggesting perturbation of photosynthesis. In conclusion, the fluorescence-based approach was useful for detecting the disturbance of specific cellular characteristics. Fluorescent probes are a useful diagnostic tool for the assessment of the impact of toxicants on specific targets of P. subcapitata algal cells.