Room Temperature, Metal-Free Synthesis of Diaryl Ethers with Use of Diaryliodonium Salts

A fast, high-yielding synthesis of diaryl ethers with use of mild and metal-free conditions has been developed. The scope includes bulky ortho-substituted diaryl ethers, which are difficult to obtain by metal-catalyzed protocols. Halo-substituents, racemization-prone amino acid derivatives, and heteroaromatics are also tolerated. The methodology is expected to be of high utility in the synthesis of complex molecules and in the pharmaceutical industry.

Amino acids profile of sugar cane spirit (cachaca), rum, and whisky

An analytical procedure for the separation and quantification of 20 amino acids in cachacas has been developed involving C18 solid phase cleanup, derivatization with o-phthalaldehyde/2-mercaptoethanol, and reverse phase liquid chromatography with fluorescence detection. The detection limit was between 0.0050 (Cys) and 0.25 (Ser) mg L-1, whereas the recovery index varies from 69.5 (Lys) to 100 (Tyr)%. Relative standard deviations vary from 1.39 (Trp) to 13.4 (Glu)% and from 3.08 (Glu) to 13.5 (His) for the repeatability and intermediate precision, respectively. From the quantitative profile of amino acids in 41 cachacas, 5 turns, and 12 whisky samples, the following order of amino acids in significant quantities is observed: Gly = Ser < Cys < Ile < His < Pro = Asp < Asn < Tyr for cachaca; Phe < Glu = Gln = Val = Ala < His = Gly Thr = Arg = Tyr < Asn Ser = Lys = Pro < Cys = Asp for rum; and Ala = Asn < Trp < Gln = His = Met = Ile = Cys < Thr < Asp Leu < Phe = Lys < Ser = Gly = Tyr = Val < Glu = Pro < Arg for whisky samples. (C) 2007 Elsevier Ltd. All rights reserved.

Efeito dos nutrientes (nitrogênio e fósforo) sobre o desenvolvimento da Gracilaria birdiae: crescimento e possível uso como biofiltro

Marine shrimp farming has grown exponentially during the last years in Brazil. In spite of the promising economical situation, this activity is facing an increasing criticism due to its environmental impact. Thus, the necessity of alternatives to mitigate environmental degradation caused by this activity. An alternative that is being studied is the policulture that is the integrated culture of two or more organisms, normally one of them a filtering organism. Among filtering organisms, macroalgae are very practicable because they are efficient in the removal of the exceeding nutrients of the water and do not leave residues in the water. Besides, the integrated culture with macroalgae allows the economical exploration of the seaweed (for the manufacture of jelly and jam, for the dairy industry, pharmaceuticals, etc.) along with possibility of a sustainable aquaculture. In the present experiment, the development of the seaweed Gracilaria birdiae, the influence and tolerance of this species to the environmental parameters, and its absorption efficiency in relation with the three kinds of macronutrients (NH4+, NO3- and PO4-3) found in the effluents of marine shrimp farming was studied. The experiment was divided in two parts: a laboratorial part and one part carried under natural conditions. The water used in the laboratory trial was collected in the shrimp ponds of Tecnarão farm and distributed in aquaria containing 20 g of G. birdiae. In the field trial, 0.5 kg of G. birdiae was inserted in PVC cages cultivated in the farm. The results of the study showed a modest growth of G. birdiae, probably due to its low tolerance to highly eutrophicated environments. However, the removal of nutrients was very expressive. Ammonia was reduced in approximately 34 %. Ortho-phosphate showed a reduction of 93.5 %. The capacity of biofiltration of the NO3- by the macro algae was of 100 %, showing that G. birdiae is a seaweed-filtered with a high level of removal for this nutrient under laboratorial conditions. In spite of the low growth of the macro algae in the experiment, the results in relation to the removal of nutrients of the water was encouraging, suggesting that this species can be an efficient biofilter and thus, a strong candidate to be used in a sustainable aquaculture

Compósitos poliméricos a base de fibras de licuri: efeitos da hibridização e do envelhecimento ambiental acelerado

The gradual replacement of conventional materials by the ones called composite materials is becoming a concern about the response of these composites against adverse environmental conditions, such as ultraviolet radiation, high temperature and moist. Also the search for new composite using natural fibers or a blend of it with synthetic fibers as reinforcement has been studied. In this sense, this research begins with a thorough study of microstructural characterization of licuri fiber, as a proposal of alternative reinforcement to polymeric composites. Thus, a study about the development of two composite laminates was done. The first one, involving only the fiber of licuri and the second comprising a hybrid composite based of fiber glass E and the fiber of licuri, in order to know the performance of the fiber when of fiber across the hybridization process. The laminates were made in the form of plates using the tereftálica ortho-polyester resin as matrix. The composite laminate made only by licuri fiber had two reinforcing fabric layers of unidirectional licuri and the hybrid composite had two reinforcing layers of unidirectional licuri fabric and three layers of fiber short glass-E mat. Finally, both laminates was exposed to aging acceleration in order to study the influence of environmental degradation involving the mechanical properties and fracture characteristics thereof. Regarding the mechanical properties of composites, these were determined through uniaxial tensile tests, uniaxial compression and three bending points for both laminates in original state, and uniaxial tensile tests and three bending points after accelerated aging. As regards the study of structural degradation due to aging of the laminates, it was carried out based on microscopic analysis and microstructure, as well as measuring weight loss. The characteristics of the fracture was performed by macroscopic and microscopic (optical and SEM) analysis. In general, the laminated composites based on fiber licuri showed some advantages in their responses to environmental aging. These advantages are observed in the behavior related to stiffness as well as the microstructural degradation and photo-oxidation processes. However, the structural integrity of this laminate was more affected in case the action of uniaxial tensile loads, where it was noted a lower rate of withholding his last resistance property

Compósito Polimérico Híbrido: Comportamento Mecãnico, Descotinuidade Geométrica e Resistência Residual

The growing demand in the use of hybrid composite materials makes it essential a better understanding of their behavior face of various design conditions, such as the presence of geometric discontinuities in the cross section of structural elements. This way, the purpose of this dissertation is a study of the mechanical response (strength and stiffness), modes (characteristics) of fracture and Residual Strength of an hybrid polymeric composite with and without a geometric discontinuity in its longitudinal section (with a reduction in the cross section) loaded by uniaxial tension. This geometric discontinuity is characterized by central holes of different diameters. The hybrid composite was fabricated as laminate (plate) and consisting of ortho-tereftalic polyester matrix reinforced by 04 outer layers of Jute fibers bidirectional fabrics and 01 central layer of E-glass bidirectional fabric. The laminate was industrially manufactured (Tecniplas Nordeste Indústria e Comércio Ltda.), obtained by the hand lay-up technique. Initially, a study of the volumetric density of the laminate was made in order to verify its use in lightweight structures. Also were performed comparative studies on the mechanical properties and fracture modes under the conditions of the specimens without the central hole and with the different holes. For evaluating the possible influence of the holes in the structural stability of the laminate, the Residual Strength of the composite was determined for each case of variation in hole diameter. As a complementary study, analyses of the macroscopic final fracture characteristic of the laminates were developed. The presence of the central hole of any sizes, negatively changed the ultimate tensile strength. Regarding the elastic modulus, moreover, the difference found between the specimens was within the range of tests displacement, showing the laminate stability related to the stiffness

Electrochemical modified electrodes based on metal-salen complexes

A general view of the electroanalytical applications of metal-salen complexes is discussed in this review. The family of Schiff bases derived from ethylenediamine and ortho-phenolic aldehydes (N,N'-ethylenebis(salicylideneiminato) - salen) and their complexes of various transition metals, such as Al, Ce, Co, Cu, Cr, Fe, Ga, Hg, Mn, Mo, Ni, and V have been used in many fields of chemical research for a wide range of applications such as catalysts for the oxygenation of organic molecules, epoxidation of alkenes, oxidation of hydrocarbons and many other catalyzed reactions; as electrocatalyst for novel sensors development; and mimicking the catalytic functions of enzymes. A brief history of the synthesis and reactivity of metal-salen complexes will be presented. The potentialities and possibilities of metal-Salen complexes modified electrodes in the development of electrochemical sensors as well as other types of sensors, their construction and methods of fabrication, and the potential application of these modified electrodes will be illustrated and discussed.

The reactivity of oytho-methoxy-substituted catechol radicals with sulfhydryl groups: Contribution for the comprehension of the mechanism of inhibition of NADPH oxidase by apocynin

Redox processes are involved in the mechanism of action of NADPH oxidase inhibitors such as diphenyleneiodonium and apocynin. Here, we studied the structure-activity relationship for apocynin and analogous ortho-methoxy-substituted catechols as inhibitors of the NADPH oxidase in neutrophils and their reactivity with peroxidase. Aiming to alter the reduction potential, the ortho-methoxy-catechol moiety was kept constant and the substituents at para position related to the hydroxyl group were varied. Two series of compounds were employed: methoxy-catechols bearing electron-withdrawing groups (MC-W) such as apocynin, vanillin, 4-nitroguaiacol, 4-cyanoguaiacol, and methoxy-catechol bearing electron-donating groups (MC-D) such as 4-methylguaiacol and 4-ethylguaiacol. We found that MC-D were weaker inhibitors compared to MD-W. Furthermore, the radicals generated by oxidation of MC-W via MPO/H(2)O(2), but not for MC-D, were able to oxidize glutathione (GSH) as verified by the formation of thiyl radicals, depletion of GSH, and recycling of the ortho-methoxy-catechols during their oxidations. The capacity of oxidizing sulfhydryl (SH) groups was also verified when ovalbumin was incubated with MC-W, but not for MC-D. Since the effect of apocynin has been correlated with inactivation of the cytosolic fractions of the NADPH oxidase complex and its oxidation during the inhibitory process develops a special role in this process, we suggest that the close relationship between the reactivity of the radicals of MC-W compounds with thiol groups and their efficacy as NADPH oxidase inhibitor could be the chemical pathway behind the mechanism of action of apocynin and should be taken into account in the design of new and specific NADPH oxidase inhibitors. (c) 2007 Elsevier B.V. All rights reserved.

Biochemical, histopathological and clinical evaluation of delayed effects caused by methamidophos isoforms and TOCP in hens: Ameliorative effects using control of calcium homeostasis

This work evaluated the potential of the isoforms of methamidophos to cause organophosphorus-induced delayed neuropathy (OPIDN) in hens. In addition to inhibition of neuropathy target esterase (NTE) and acetylcholinesterase (AChE), calpain activation, spinal cord lesions and clinical signs were assessed. The isoforms (+)-, (+/-)- and (-)-methamidophos were administered at 50 mg/kg orally; tri-ortho-cresyl phosphate (TOCP) was administered (500 mg/kg, po) as positive control for delayed neuropathy. The TOCP hens showed greater than 80% and approximately 20% inhibition of NTE and AChE in hen brain, respectively. Among the isoforms of methamidophos, only the (+)-methamidophos was capable of inhibiting NTE activity (approximately 60%) with statistically significant difference compared to the control group. Calpain activity in brain increased by 40% in TOCP hens compared to the control group when measured 24h after dosing and remained high (18% over control) 21 days after dosing. Hens that received (+)-methamidophos had calpain activity 12% greater than controls. The histopathological findings and clinical signs corroborated the biochemical results that indicated the potential of the (+)-methamidophos to be the isoform responsible for OPIDN induction. Protection against OPIDN was examined using a treatment of 2 doses of nimodipine (1 mg/kg, i.m.) and one dose of calcium gluconate (5 mg/kg, iv.). The treatment decreased the effect of OPIDN-inducing TOCP and (+)-methamidophos on calpain activity, spinal cord lesions and clinical signs. (C) 2012 Elsevier B.V. All rights reserved.

Qualidade de vida de pacientes com deformidade dentofacial

In the last decade, an increasing number of studies focusing on the impact of oral deformities on quality of life have been published. However, the evaluation of patients at different phases of the treatment has not been performed. Therefore, the purpose of this study was to determine the impact that dentofacial deformities have on patients` quality of life, as well as the influence exerted by social, economic, demographic and orthodontic factors, type and severity of malocclusion. A bicentric study - of the cross-sectional type of repeated panels - involving two cities - Natal and Rio de Janeiro - was carried out. A total of 227 patients participated in the study: 71 patients in the initial phase of the treatment (before any orthosurgical procedure), 115 patients in the pre-surgical (with braces) phase and 41 patients in the postoperative phase. The quality of life was measured using the Orthognatic Quality of Life Questionnnaire - OQLQ, translated and validated into Portuguese. The normative and aesthetic need for treatment was assessed with the Index of Orthodontic Treatment Need (IOTN) and the Dental Aesthetic Index (DAI); the social, economic and demographic factors, the type of service and malocclusion were also assessed. The data were analyzed through χ2/ Fisher`s exact test to seek the association between the nominal categorical variables in the three phases of treatment, Mann Whitney and Kruskal-Wallis test for gauging the existence of significant differences between two and three groups regarding each domain of OQLQ, respectively. For all tests, it was adopted a significance level of 5%. There was a statistically significant difference (p <0.001) in the general scores of OQLQ and in the domains of social aspects, facial aesthetics and oral function, when the "postoperative group" was compared to the "initial" and "orthodontic preparation" groups. Women, single, aged between 31 and 59 and living in Natal had the greatest impact on quality of life among patients in the "orthodontic preparation" group. Only the variable "income" (2 to 3 minimum wages), for the "initial" group, and gender (female) for the "postoperative" group, showed significant association with quality of life. The normative variable IOTN (DHC and AC) showed significant association with the OQLQ for the "initial" group, and the IOTN-AC-auto in the group of orthodontic preparation, being less important to women. We conclude that the ortho-surgical therapy has positive effects on quality of life after orthognathic surgery

Scattering of positronium by H, He, Ne, and Ar

The low-energy scattering of the ortho-positronium (Ps) by H, He, Ne, and Ar atoms has been investigated in the coupled-channel framework by using a recently proposed time-reversal symmetric non-local electron-exchange model potential with a single parameter C. For H and He, we use a three-Ps-state coupled-channel model and, for Ar and Ne, we use a static-exchange model. The sensitivity of the results is studied with respect to the parameter C. Present low-energy cross-sections for He, Ne and Ar are in good agreement with experiment. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Resonances in positronium-rubidium and positronium-cesium scattering

Scattering of ortho positronium (Ps) by cesium and rubidium atoms has been investigated employing a three-Ps-state coupled-channel model with Ps(1s,2s,2p) states using a time-reversal-symmetric regularized electron-exchange model potential. We find a narrow S-wave singlet resonance at 5.057 eV of width 0.003 eV in the Ps-Rb system and at 5.067 eV of width 0.003 eV in the Ps-Cs system. Singlet P-wave resonances in both systems are found at 5.3 eV of width 0.4 eV. Singlet D-wave structures are found at 5.4 eV in both systems. The pronounced P- and D-wave resonances in these systems lead to easily detectable local minima in the low-energy elastic cross sections. We also report results for elastic and Ps-excitation cross sections for Pa scattering by Rb and Cs. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Positronium-positronium interaction: resonance, scattering length, and Bose-Einstein condensation

The low-energy scattering of ortho positronium (Ps) by ortho Ps has been studied in a full quantum mechanical coupled-channel approach. In the singlet channel (total spin s(T) = 0) we find S- and P-wave resonances at 3.35 eV (width 0.02 eV) and 5.05 eV (width 0.04 eV), respectively, and a binding of 0.43 eV of Ps(2). The scattering length for s(T) = 0 is 3.95 Angstrom and for s(T) = 2 is 0.83 Angstrom. The small s(T) = 2 scattering length makes the spin-polarized ortho Ps atoms an almost noninteracting ideal gas which may undergo Bose-Einstein condensation. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Positronium atom scattering by H-2 in a coupled-channel framework

The scattering of ortho-positronium (Ps) by H-2 has been investigated using a three-Ps-state (Ps(1s,2s, 2p)H-2(X (1)Sigma(g)(+))) coupled-channel model and using the Born approximation for higher excitations and ionization of Ps and B (1)Sigma(u)(+) and b (3)Sigma(u)(+) excitations of H-2. We employ a recently proposed time-reversal-symmetric non-local electron-exchange model potential. We present a calculational scheme for solving the body-frame fixed-nuclei coupled-channel scattering equations for Ps-H-2, which simplifies the numerical solution technique considerably. Ps ionization is found to have the leading contribution to target-elastic and all target-inelastic processes. The total cross sections at low and medium energies are in good agreement with experiment.

Effect of electron exchange in positronium-hydrogen scattering

The elastic and inelastic scattering of ortho-positronium (Ps) by the hydrogen atom have been investigated using a three-Ps-state close-coupling approximation. The higher (n greater than or equal to 3) excitations and ionization of the Ps atom are treated within the framework of the Born approximation. In both cases the effect of electron exchange has been included by a parameter-free nonlocal model potential derived from an antisymmetrization of the wavefunction followed by the removal of nonorthogonality. Calculations are reported of scattering lengths,phase shifts, and of elastic, Ps excitation, and total cross sections. The trend of present target elastic total cross section agrees qualitatively with available experimental results on Ps-impact scattering.

On the V-type asteroids outside the Vesta family - II. Is (21238) 1995 WV7 a fragment of the long-lost basaltic crust of (15) Eunomia?

Context. The V-type asteroids are associated with basaltic composition. Apart from ( 1459) Magnya, an asteroid that is clearly dynamically and mineralogically unconnected to the Vesta family, all currently known V-type asteroids are either members of the Vesta family, or are hypothesized to be former members of the dynamical family that migrated to their current orbital positions. The recent identification of ( 21238) 1995 WV7 as a V-type asteroid introduces the possibility that a second basaltic asteroid not connected with the Vesta family exists. This asteroid is on the opposite side of the 3: 1 mean motion resonance with respect to Vesta, and it would be very unlikely that a member of the Vesta family of its size (D > 5km) migrating via either the Yarkovsky effect or repeated close encounters with Vesta survived the passage through such a resonance.Aims. In this work we investigate the possibility that ( 21238) 1995 WV7 originated as a fragment of the parent body of the Eunomia family and then migrated via the interplay of the Yarkovsky effect and some powerful nonlinear secular resonances, such as the (s - s(6)) - ( g(5) - g(6)). If (15) Eunomia is, as claimed, a differentiated object whose originally pyroxene-enriched crust layer was lost in a collision that either created the Eunomia family or preceded its formation, can (21238) be a fragment of its long-lost basaltic crust that migrated to the current position?Methods. We mapped the phase space around (21238) and determined which of the nonlinear secular resonances that we identified are stronger and more capable of having caused the current difference in proper i between (21238) and members of the Eunomia family. We simulated the Yarkovsky effect by using the SWIFT-RMVSY integrator.Results. Our results suggest that it is possible to migrate from the Eunomia dynamical family to the current orbital location of ( 21238) via the interplay of the Yarkovsky effect and the (s - s6) - (g5 - g6) nonlinear secular resonance, on time-scales of at least 2.6 Gyr.Conclusions. (15) Eunomia might be the third currently known parent body for V-type asteroids.