Scorpionate complexes as catalysts for alkane functionalization

A survey of the scorpionate tris(pyrazolyl)methane complexes synthesized by our group is presented, as well as their structural features and catalytic applications toward the funtionalization of linear and cyclic light alkanes.

Renormalization-group constraints on Yukawa alignment in multi-Higgs-doublet models

We write down the renormalization-group equations for the Yukawa-coupling matrices in a general multi-Higgs-doublet model. We then assume that the matrices of the Yukawa couplings of the various Higgs doublets to right-handed fermions of fixed quantum numbers are all proportional to each other. We demonstrate that, in the case of the two-Higgs-doublet model, this proportionality is preserved by the renormalization-group running only in the cases of the standard type-I, II, X, and Y models. We furthermore show that a similar result holds even when there are more than two Higgs doublets: the Yukawa-coupling matrices to fermions of a given electric charge remain proportional under the renormalization-group running if and only if there is a basis for the Higgs doublets in which all the fermions of a given electric charge couple to only one Higgs doublet.

Molybdenum Complexes Bearing the Tris(1-pyrazolyl)methanesulfonate Ligand: Synthesis, Characterization and Electrochemical Behaviour

The tris(1-pyrazolyl)methanesulfonate lithium salt Li(Tpms) [Tpms = SO3C(pz)(3)-] reacts with [Mo(CO)(6)] in NCMe heated at reflux to yield Li[Mo(Tpms)(CO)(3)] (1), which, upon crystallization from thf, forms the coordination polymer [Mo(Tpms)(CO)(2)(mu-CO)Li(thf)(2)](n) (2). Reaction of 1 with I-2, HBF4 or AgBF4 yields [Mo(Tpms)I(CO)(3)] (3), (Mo(Tpms)-H(CO)(3)] (5) or (Mo(Tpms)O-2](2)(mu-O) (7), respectively. The high-oxidation-state dinuclear complexes [{Mo(Tpms)O(mu-O)}(2)] (4) and [{Mo(tpms)OCl)(2)](mu-O) (6) are formed upon exposure to air of solutions of 3 and 5, respectively. Compounds 1-7, which appear to be the first tris(pyrazolyl)methanesulfonate complexes of molybdenum to be reported, were characterized by IR, H-1 and C-13 NMR spectroscopy, ESI-MS, elemental analysis, cyclic voltammetry and, in the cases of Li(Tpms) and compounds 2, 4.2CH(3)CN, 6.6CHCl(3) and 7, by X-ray diffraction analyses. Li(Tpms) forms a 1D polymeric structure (i.e., [Li(tpms)](n)} with Tpms as a tetradentate N2O2 chelating ligand that bridges two Li cations with distorted tetrahedral coordination. Compound 2 is a 1D coordination polymer in which Tpms acts as a bridging tetradentate N3O ligand and each Li(thf)(2)(+) moiety is coordinated by one bridging CO ligand and by the sulfonyl group of a contiguous monomeric unit. In 4, 6 and 7, the Tpms ligand is a tridentate chelator either in the NNO (in 4) or in the NNN (in 6 and 7) fashion. Complexes 1, 3 and 5 exhibit, by cyclic voltammetry, a single-electron oxidation at oxidation potential values that indicate that the Tpms ligand has an electron-donor character weaker than that of cyclopentadienyl.

Assessment of fungal contamination in a group of Lisbon's gymnasiums with a swimming pool

The study’s main purpose was the assessment of the environmental fungal contamination, the exploration of possible associations between related environmental variables and the study of the relationship between fungal contamination of air and surfaces. A descriptive study was developed based upon air and surfaces monitoring for fungal contamination in ten indoor gymnasiums with a swimming pool located in Lisbon’s urban area. Fifty 200 litres air samples and 120 surface swabs were collected. Surfaces samples were collected before and after cleaning and disinfection and temperature and relative humidity values were registered during the collection period. Twenty five different species of fungi were identified in the air samples, being the three most commonly isolated genera the following: Cladosporium (36.6%), Penicillium (19.0%) and Aspergillus (10.2%). Thirty-seven different species of fungi were identified in the surface samples. Fusarium sp. was the most frequent genera before (19.1%) and after (17.2%) cleaning and disinfection. There was a significant association between the numbers of visitors and the fungal contamination determined in the surface samples (p<0.05). There was no significant association (p>0.05) between the contamination encountered in the air samples and the one registered in the surface samples and between the fungal contamination and the temperature or relative humidity measured on location. The data obtained enabled the assessment of the establishment’s fungal contamination and led the authors to conclude, consequently, that physical activity, which generally promotes health, can in fact be challenged by this factor.

Rearranjos 3-aza-cope de N-alil-N-sililoxi enaminas

O rearranjo [3,3]-sigmatrópico térmico (180ºC) de diferentes N-alil-N-sililoxi enaminas foi estudado. Os respectivos produtos de rearranjo (éteres de óxima) foram obtidos com rendimentos elevados (80%). A regiosselectividade, [3,3] vs [1,3], e a diastereosselectividade do processo foram elevadas, superior a 99% e aproximadamente 80%, respectivamente. Foi demonstrada a importância do grupo sililoxilo na promoção do rearranjo face a substratos sem este tipo de substituição. Posteriormente, foi estudada a possibilidade de aceleração aniónica deste tipo de rearranjo por formação de oxianião ligado ao átomo de azoto. A estratégia seguida para a formação do mesmo, consistiu na O-dessililação de diferentes N-alil-N-sililoxi enaminas tendo-se obtido as nitronas correspondentes ou produtos de ciclização. Num exemplo envolvendo um derivado de isoxazole-5-(2H)-ona foi observado um aumento de velocidade do rearranjo por reacção com ião etoxilo. Este aumento de velocidade foi atribuído à abertura de anel do N-O éster cíclico para o N-oxianião, seguida de rearranjo e posterior fecho. Métodos alternativos de aceleração do rearranjo por geração de carga positiva, parcial ou completa, no átomo de azoto levaram apenas à dessililação das N-alil-N-sililoxi enaminas. ABSTRACT - [3,3]-sigmatropic rearrangement of a variety of N-allyl-N-silyloxy enamines was studied. The corresponding rearrangement products (oxime-ethers) were obtained in high yields (80%). High regioselectivity, [3,3] vs [1,3] (> 99%) and in appropriate cases, diastereoselectivity (80%) were observed. The importance of the silyloxy group in promoting the rearrangement, in relation to substrates lacking this functionality, is underlined. The possible anionic acceleration of the rearrangements was next examined by O-desilylation the N-silyloxy group bonded to the nitrogen. Attempted generation of these species however, was found to lead either to the corresponding nitrones or to cyclization products. In one particular example involving an isoxazol-5-(2H)-one derivative rate enhancement of rearrangement was indeed observed with ethoxide ion. It is tentatively attributed to ring opening of the cyclic N-O ester to the N-oxyanion ethyl ester followed by rearrangement and subsequent reclosure. Alternative methods to accelerate the process by generating a partial or complete positive charge on the nitrogen atom led only to desilylation.

From efficiency to optimality in proportional reinsurance under group correlation

Based on our recent discovery of closed form formulae of efficient Mean Variance retentions in variable quota-share proportional reinsurance under group correlation, we analyzed the influence of different combination of correlation and safety loading levels on the efficient frontier, both in a single period stylized problem and in a multiperiod one.

Cyclic deformation of bidisperse two-dimensional foams

In-plane deformation of foams was studied experimentally by subjecting bidisperse foams to cycles of traction and compression at a prescribed rate. Each foam contained bubbles of two sizes with given area ratio and one of three initial arrangements: sorted perpendicular to the axis of deformation (iso-strain), sorted parallel to the axis of deformation (iso-stress), or randomly mixed. Image analysis was used to measure the characteristics of the foams, including the number of edges separating small from large bubbles N-sl, the perimeter (surface energy), the distribution of the number of sides of the bubbles, and the topological disorder mu(2)(N). Foams that were initially mixed were found to remain mixed after the deformation. The response of sorted foams, however, depended on the initial geometry, including the area fraction of small bubbles and the total number of bubbles. For a given experiment we found that (i) the perimeter of a sorted foam varied little; (ii) each foam tended towards a mixed state, measured through the saturation of N-sl; and (iii) the topological disorder mu(2)(N) increased up to an "equilibrium" value. The results of different experiments showed that (i) the change in disorder, Delta mu(2)(N), decreased with the area fraction of small bubbles under iso-strain, but was independent of it under iso-stress; and (ii) Delta mu(2)(N) increased with Delta N-sl under iso-strain, but was again independent of it under iso-stress. We offer explanations for these effects in terms of elementary topological processes induced by the deformations that occur at the bubble scale.

Children visual screening protocol: validation by a focus group panel of experts

Screening programs, particularly the inclusion of specific orthoptic tests to detect visual abnormalities, varies among countries. This study aims to: 1) describes expert perception of issues related with children visual screening; 2) identify specific orthoptic tests to detect visual abnormalities in children visual screening.

5' and 3' UTR thymidylate synthase polymorphisms modulate the risk of colorectal cancer independently of the intake of methyl group donors

Thymidylate synthase, as a rate-limiting step in DNA synthesis, catalyses the conversion of dUMP into dTMP using 5,10-methylenotetrahydrofolate as the methyl donor. Two polymorphisms have been described in this gene: a repeat polymorphism in the 5' promoter enhancer region (3R versus 2R) and a 6 bp deletion in the 3' unstranslated region. Both of these may affect protein levels. The present case control study was aimed at investigating the influence of these two polymorphisms on the development of colorectal cancer (CRC), as well as their potential interaction with folate, vitamin B6 and vitamin B12 intake. A total of 196 cases and 200 controls, matched for age and sex distribution, were included in the study. No association was found between CRC and the 28 bp repeat polymorphism, but it was observed that individuals with the 6 bp/del and del/del genotypes had a significantly lower risk of developing the disease (OR=0.47; 95% CI 0.30-0.72). A combined genotype (2R/2R; 6 bp/del+del/del) was also found, which was associated with an even lower risk of developing of the disease (OR=0.42; 95% CI 0.26-0.69). No significant interaction between these polymorphisms and vitamin intake was observed. These results indicate for the first time that the 6 bp/del allele might be a protective factor in the development of CRC, independent of the intake of methyl group donors.

The influence of experience and training in a group of novice observers: a jackknife alternative free-response receiver operating characteristic analysis

Purpose - The study evaluates the pre- and post-training lesion localisation ability of a group of novice observers. Parallels are drawn with the performance of inexperienced radiographers taking part in preliminary clinical evaluation (PCE) and ‘red-dot’ systems, operating within radiography practice. Materials and methods - Thirty-four novice observers searched 92 images for simulated lesions. Pre-training and post-training evaluations were completed following the free-response the receiver operating characteristic (FROC) method. Training consisted of observer performance methodology, the characteristics of the simulated lesions and information on lesion frequency. Jackknife alternative FROC (JAFROC) and highest rating inferred ROC analyses were performed to evaluate performance difference on lesion-based and case-based decisions. The significance level of the test was set at 0.05 to control the probability of Type I error. Results - JAFROC analysis (F(3,33) = 26.34, p < 0.0001) and highest-rating inferred ROC analysis (F(3,33) = 10.65, p = 0.0026) revealed a statistically significant difference in lesion detection performance. The JAFROC figure-of-merit was 0.563 (95% CI 0.512,0.614) pre-training and 0.677 (95% CI 0.639,0.715) post-training. Highest rating inferred ROC figure-of-merit was 0.728 (95% CI 0.701,0.755) pre-training and 0.772 (95% CI 0.750,0.793) post-training. Conclusions - This study has demonstrated that novice observer performance can improve significantly. This study design may have relevance in the assessment of inexperienced radiographers taking part in PCE or commenting scheme for trauma.

Assessing the behaviour of RC beams subject to significant gravity loads under cyclic loads

Gravity loads can affect a reinforced concrete structure's response to seismic actions, however, traditional procedures for testing the beam behaviour do not take this effect into consideration. An experimental campaign was carried out in order to assess the influence of the gravity load on RC beam connection to the column subjected to cyclic loading. The experiments included the imposition of a conventional quasi-static test protocol based on the imposition of a reverse cyclic displacement history and of an alternative cyclic test procedure starting from the gravity load effects. The test results are presented, compared and analysed in this paper. The imposition of a cyclic test procedure that included the gravity loads effects on the RC beam ends reproduces the demands on the beams' critical zones more realistically than the traditional procedure. The consideration of the vertical load effects in the test procedure led to an accumulation of negative (hogging) deformation. This phenomenon is sustained with the behaviour of a portal frame system under cyclic loads subject to a significant level of the vertical load, leading to the formation of unidirectional plastic hinges. In addition, the hysteretic behaviour of the RC beam ends tested was simulated numerically using the nonlinear structural analysis software - OpenSees. The beam-column model simulates the global element behaviour very well, as there is a reasonable approximation to the hysteretic loops obtained experimentally. (C) 2013 Elsevier Ltd. All rights reserved.

The key role of coligands in novel ruthenium(II)-cyclopentadienyl bipyridine derivatives: Ranging from non-cytotoxic to highly cytotoxic compounds

A new family of eight ruthenium(II)-cyclopentadienyl bipyridine derivatives, bearing nitrogen, sulfur, phosphorous and carbonyl sigma bonded coligands, has been synthesized. Compounds bearing nitrogen bonded coligands were found to be unstable in aqueous solution, while the others presented appropriate stabilities for the biologic assays and pursued for determination of IC50 values in ovarian (A2780) and breast (MCF7 and MDAMB231) human cancer cell lines. These studies were also carried out for the [5: HSA] and [6: HSA] adducts (HSA = human serum albumin) and a better performance was found for the first case. Spectroscopic, electrochemical studies by cyclic voltammetry and density functional theory calculations allowed us to get some understanding on the electronic flow directions within the molecules and to find a possible clue concerning the structural features of coligands that can activate bipyridyl ligands toward an increased cytotoxic effect. X-ray structure analysis of compound [Ru(eta(5)-C5H5)(bipy)(PPh3)][PF6] (7; bipy = bipyridine) showed crystallization on C2/c space group with two enantiomers of the [Ru(eta(5)-C5H5)(bipy)(PPh3)](+) cation complex in the racemic crystal packing. (C) 2015 Elsevier Inc All rights reserved.

Group-to-group bidirectional Wi-Fi direct communication with two relay nodes

The current capabilities of mobile phones in terms of communication, processing and storage, enables its use to form autonomous networks of devices that can be used in case of collapse or inexistent support from a communication infrastructure. In this paper, we propose a network configuration of nodes that provides high-speed bidirectional device-to-device communication, with symmetrical data transfer rates, in Wi-Fi Direct multi-group scenarios, without using performance hindering broadcasts. Copyright © 2015 ICST.

The key role of coligands in novel ruthenium(II)-cyclopentadienyl bipyridine derivatives: ranging from non-cytotoxic to highly cytotoxic compounds

A new family of eight ruthenium(II)-cyclopentadienyl bipyridine derivatives, bearing nitrogen, sulfur, phosphorous and carbonyl sigma bonded coligands, has been synthesized. Compounds bearing nitrogen bonded coligands were found to be unstable in aqueous solution, while the others presented appropriate stabilities for the biologic assays and pursued for determination of IC50 values in ovarian (A2780) and breast (MCF7 and MDAMB231) human cancer cell lines. These studies were also carried out for the [5: HSA] and [6: HSA] adducts (HSA=human serum albumin) and a better performance was found for the first case. Spectroscopic, electrochemical studies by cyclic voltammetry and density functional theory calculations allowed us to get some understanding on the electronic flow directions within the molecules and to find a possible clue concerning the structural features of coligands that can activate bipyridyl ligands toward an increased cytotoxic effect. X-ray structure analysis of compound [Ru(η(5)-C5H5)(bipy)(PPh3)][PF6] (7; bipy=bipyridine) showed crystallization on C2/c space group with two enantiomers of the [Ru(η(5)-C5H5)(bipy)(PPh3)](+) cation complex in the racemic crystal packing.