New reductive addition of hard nucleophiles to 6,7-bis(methylsulfanyl)-1,4-dihydro-1,4-methanonaphthalene-5,8-dione

A new reaction mode of 6,7-bis(methylsulfanyl)-1,4-dihydro-1,4-methanonaphthalene-5,8-dione 1 with the hard nucleophiles sodium benzene- or methane-sulfinate and cyanide, in DMSO, at room temperature, leads to the unexpected hydroquinonoid products 3a-c. All the data are in agreement with a mechanistic pathway involving the initial attack of the hard nucleophile onto the hard carbonyl group, followed by a symbiotic re-attack of the oxygen on the incoming group. In the case of soft nucleophiles, reaction on the olefinic carbon of the enedione system is preferential.

Stretching of BDT-gold molecular junctions: thiol or thiolate termination?

It is often assumed that the hydrogen atoms in the thiol groups of a benzene-1,4-dithiol dissociate when Au-benzene-1,4-dithiol-Au junctions are formed. We demonstrate, by stability and transport property calculations, that this assumption cannot be made. We show that the dissociative adsorption of methanethiol and benzene-1,4-dithiol molecules on a flat Au(111) surface is energetically unfavorable and that the activation barrier for this reaction is as high as 1 eV. For the molecule in the junction, our results show, for all electrode geometries studied, that the thiol junctions are energetically more stable than their thiolate counterparts. Due to the fact that density functional theory (DFT) within the local density approximation (LDA) underestimates the energy difference between the lowest unoccupied molecular orbital and the highest occupied molecular orbital by several electron-volts, and that it does not capture the renormalization of the energy levels due to the image charge effect, the conductance of the Au-benzene-1,4-dithiol-Au junctions is overestimated. After taking into account corrections due to image charge effects by means of constrained-DFT calculations and electrostatic classical models, we apply a scissor operator to correct the DFT energy level positions, and calculate the transport properties of the thiol and thiolate molecular junctions as a function of the electrode separation. For the thiol junctions, we show that the conductance decreases as the electrode separation increases, whereas the opposite trend is found for the thiolate junctions. Both behaviors have been observed in experiments, therefore pointing to the possible coexistence of both thiol and thiolate junctions. Moreover, the corrected conductance values, for both thiol and thiolate, are up to two orders of magnitude smaller than those calculated with DFT-LDA. This brings the theoretical results in quantitatively good agreement with experimental data.

Síntese de nanopartículas de prata suportadas sobre nanotubos de carbono de paredes múltiplas para eletrooxidação de benzeno

Silver nanoparticles (Ag) were deposited on multi-walled carbon nanotube by eletroless. The hybrid Ag/MWCNT was used in the modification of glassy carbon electrode (GC) surface. The electrochemical characterization confirmed the presence of Ag in the nanocomposite has been showed that the synthesis was successful. The GC electrode modified with Ag/MWCNT film was evaluated for electro-oxidation of benzene. The electrochemical behavior presented an improvement on the catalytic surface in relation to non-modified GC electrode. The anodic peak current increased the magnitude in three times when compared with the CG electrode modified only with MWCNT

Redução de consumo de energia eletrica a partir de reaproveitamento de energia termica com uso de ciclo rankine orgânico

This paper is proposed the usage of an Organic Rankine Cycle (ORC) along with waste heat recovery from an inconstant heat source. This method of waste heat recovery with intermittent heat source is part of a technical viability study. This paper also brings up the usage of thermal energy storage as heat source for the ORC. This paper is based on a heat treatment company study in which a natural gas furnace is explored. Data such as mass flow, temperature and specific waste gas heat from this furnace are used through calculations. Calculations are made also based on furnace cycles. This viability study considers a series of working fluids such as ammonia, benzene, R113 and R134a. Results point out that ORC with out thermal storage and using refrigerant fluid ammonia is the best alternative

Avaliação do efeito tóxico do herbicida trifluralina por meio do estudo histológico e histoquímico do intestino médio do diplópodo Rhinocricus padbergi

Currently the use of pesticides in agriculture is widespread due to their high effectiveness in combating pests, weeds and diseases leading to better productivity and economical performance in agricultural area. The use of pesticides affects the whole world and their use is often performed in an improper and indiscriminate way and for long periods. Several studies have been carried out in order to verify the presence of pesticides in nature, with worrying results. The presence of higher levels of pesticides and their degradation products in soil and surface and groundwater have indicated increasing contamination. Among the most widely used pesticides, herbicides are present and among these trifluralin has occupied an important place due to its widespread use; it is an herbicide originated from benzene derivatives belonging to dinitroanilines family; it is classified as belonging to group C, being possibly carcinogenic for humans, present a high persistence in soil as a result of its low mobility and therefore may affect local edaphic fauna. Diplopods belong to a group of invertebrates considered important in the soil dynamics; due to their close contact with it, these animals can be used as bioindicators of substrates toxicity. This study aimed to expose diplopod specimens of the species R. padbergi to different concentrations of trifluralin and therefore it was mounted five bioassays containing soil from the site where animals were collected (control group) and the same soil mixed to different concentrations of trifluralin herbicide (concentration recommended for agriculture use, that is, the dose recommended by the producer 0.0534g/m2, double, haft and quarter of this dose), animals were exposed for 7 and 90 days. During the entire period of exposure (90 days), it was observed that the number of animals in the control bioassay remained stable until the 5th week, presenting only... (Complete abstract click electronic access below)

Efeito fitotóxico e potencial remediador de três espécies vegetais contaminadas com benzeno

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Inorganic elemental analysis and identification of residual monomers released from different glass ionomer cements in cell culture medium

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Identificação e caracterização de fungos melanizados com potencial de degradação de tolueno

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Contaminação do lençol freático por hidrocarbonetos na região de Avaré - SP

Pós-graduação em Engenharia Civil e Ambiental - FEB

Distribuição de LNAPL na zona não saturada em solos tropicais, no município de Rio Claro/SP

Pós-graduação em Geociências e Meio Ambiente - IGCE

Isolamento de cepas bacterianas degradadoras de hidrocarbonetos aromáticos

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Avaliação do processo de contaminação e remediação de água subterrânea por hidrocarbonetos

Pós-graduação em Engenharia Civil e Ambiental - FEB

Investigação dos métodos de separação, uso e aplicação da Lignina proveniente da biomassa lignocelulósica

This study investigated the main methods of separation of components of lignocellulosic biomass, with an emphasis on obtaining lignin and its application. The work was developed based on the concept of Biorefinery proposing full use of renewable raw materials and / or the use of lignocellulosic agricultural residues by biochemical or biotechnological conversion in obtaining high value added products with minimal environmental impact. From this premise, a literature review was performed in refereed journal articles and theses in order to gather enough material for critical analysis of usual and alternative methods in the literature. When researching methods that add value to lignin, it was found that with the technology found today, the cost required to have a degree of competitiveness is still too high, preventing much of the process. However, the isolated lignin can be used as raw material in the production of numerous types of biocomposites and polymers and other products such as phenols, benzene, dispersants, vanillin, emulsifying agents, antioxidants, pesticides, fertilizers, charcoal, concrete additives, among others. As an industrial production level is necessary, because the consumption of biomass will only grow over the years, it is necessary that new methods or technologies to be created in order to facilitate the extensive use of lignocellulosic biomass

Enhanced Polymer Grafting from Multiwalled Carbon Nanotubes through Living Anionic Surface-Initiated Polymerization

Anionic surface-initiated polymerization of ethylene oxide and styrene has been performed using multiwalled carbon nanotubes (MWNTs) functionalized with anionic initiators. The surface of MWNTs was modified via covalent attachment of precursor anions such as 4-hydroxyethyl benzocyclobutene (BCBEO) and 1-benzocyclobutene-1′-phenylethylene (BCB-PE) through Diels-Alder cycloaddition at 235 °C. Surface-functionalized MWNTs-g-(BCB-EO) n and MWNTs-g-(BCB-PE) n with 23 and 54 wt % precursor initiators, respectively, were used for the polymerizations. Alkoxide anion on the surface of MWNTs-g-(BCB-EO) n was generated through reaction with potassium triphenylmethane for the polymerization of ethylene oxide in tetrahydrofuran and phenyl substituted alkyllithium was generated from the surface of MWNTs-g-(BCB-PE) n using sec-butyllithium for the polymerization of styrene in benzene. In both cases, the initiation was found to be very slow because of the heterogeneous reaction medium. However, the MWNTs gradually dispersed in the reaction medium during the polymerization. A pale green color was noticed in the case of ethylene oxide polymerization and the color of initiator as well as the propagating anions was not discernible visually in styrene polymerization. Polymer grafted nanocomposites, MWNTs-g-(BCB-PEO) n and MWNTs-g-(BCB-PS) n containing a very high percentage of hairy polymer with a small fraction of MWNTs (<1 wt %) were obtained. The conversion of ethylene oxide and the weight percent of PEO on the surface of the MWNTs increased with increasing reaction time indicating a controlled polymerization. The polymer-grafted MWNTs were characterized using FTIR, 1H NMR, Raman spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and transmission electron microscopy (TEM). Size exclusion chromatography of the polymer grafted MWNTs revealed broad molecular weight distributions (1.3 < Mw/Mn < 1.8) indicating the presence of different sizes of polymer nanocomposites. The TEM images showed the presence of thick layers of polymer up to 30 nm around the MWNTs. The living nature of the growing polystyryllithium was used to produce diblock copolymer grafts using sequential polymerization of isoprene on the surface of MWNTs.

Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry Characterization of Primary Amine End-Functionalized Polystyrene and Poly(methyl methacrylate) Synthesized by Living Anionic Polymerization Techniques

The reaction of living anionic polymers with 2,2,5,5-tetramethyl-1-(3-bromopropyl)-1-aza-2,5- disilacyclopentane (1) was investigated using coupled thin layer chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Structures of byproducts as well as the major product were determined. The anionic initiator having a protected primary amine functional group, 2,2,5,5-tetramethyl- 1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane (2), was synthesized using all-glass high-vacuum techniques, which allows the long-term stability of this initiator to be maintained. The use of 2 in the preparation of well-defined aliphatic primary amine R-end-functionalized polystyrene and poly(methyl methacrylate) was investigated. Primary amino R-end-functionalized poly(methyl methacrylate) can be obtained near-quantitatively by reacting 2 with 1,1-diphenylethylene in tetrahydrofuran at room temperature prior to polymerizing methyl methacrylate at -78 °C. When 2 is used to initiate styrene at room temperature in benzene, an additive such as N,N,N',N'- tetramethylethylenediamine is necessary to activate the polymerization. However, although the resulting polymers have narrow molecular weight distributions and well-controlled molecular weights, our mass spectra data suggest that the yield of primary amine α-end-functionalized polystyrene from these syntheses is very low. The majority of the products are methyl α-end-functionalized polystyrene.