Complex molecule formation in grain mantles

Context. Complex molecules such as ethanol and dimethyl ether have been observed in a number of hot molecular cores and hot corinos. Attempts to model the molecular formation process using gas phase only models have so far been unsuccessful. Aims. To demonstrate that grain surface processing is a viable mechanism for complex molecule formation in these environments. Methods. A variable environment parameter computer model has been constructed which includes both gas and surface chemistry. This is used to investigate a variety of cloud collapse scenarios. Results. Comparison between model results and observation shows that by combining grain surface processing with gas phase chemistry complex molecules can be produced in observed abundances in a number of core and corino scenarios. Differences in abundances are due to the initial atomic and molecular composition of the core/corino and varying collapse timescales. Conclusions. Grain surface processing, combined with variation of physical conditions, can be regarded as a viable method for the formation of complex molecules in the environment found in the vicinity of a hot core/corino and produce abundances comparable to those observed.

Desidratação/oxidação seletiva de metanol recorrendo a catalisadores heterogéneos para a obtenção de biocombustíveis (DME e DMM)

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

Methane conversion reactions on Ni catalysts promoted with Rh: Influence of support

Ni catalysts supported on gamma-Al(2)O(3) and Mg(Al)O were prepared with and without Rh as a promoter and tested in the reforming of methane in the presence of excess methane, simulating a model biogas. The effects of adding synthetic air on the methane conversion and the formation of carbon were assessed. The catalysts were characterized by X-ray spectroscopy (EDS), surface area (BET), X-ray diffraction (XRD), Temperature-programmed reduction (TPR), X-ray absorption near-edge structure (XANES) and XPD. The results showed that in catalysts without Rh, the Ni interacts strongly with the supports, showing high reduction temperatures in TPR tests. The addition of Rh increased the amount of reducible Ni and facilitated the reduction of the species interacting strongly with the support. In the catalytic tests, the samples promoted with Rh suffered higher carbon deposition. The in situ XPD suggested that on the support gamma-Al(2)O(3), the presence of Rh probably led to a segregation of Ni species with time on stream, leading to carbon deposition. On the support MgAlO, the presence of Rh improved the dispersion of Ni, by reducing the Ni(0) crystallite size, suggesting that in this case the carbon deposition was due to a favoring of CH(4) decomposition by Rh. (C) 2011 Elsevier B.V. All rights reserved.

FT-IR investigation of Ion association in plasticized solid polymer electrolytes

FT-IR spectroscopy has been utilized to monitor ion association in plasticized solid polymer electrolytes (SPEs). The SPEs were prepared from a random copolymer of ethylene oxide (EO) and propylene oxide (PO) and the salt lithium trifluoromethanesulfonate (lithium triflate, LiTf). Tetraethylene glycol dimethyl ether (tetraglyme) and N,N‘-dimethylformamide (DMF) were chosen as model plasticizers. Despite having a similar dielectric constant to that of the polymer host, ε ~ 5, the incorporation of tetraglyme into the SPEs resulted in increased ion association. The addition of a higher dielectric constant solvent , DMF, ε = 36.7, resulted in decreased ion association in the SPE. The effects of salt concentration (0.05−1.25 mol dm^-3) and temperature (25−100 °C) upon ion association in SPEs were also investigated. At low salt concentrations, ion association was found to increase with temperature, however, at 1.25 mol dm^-3 the temperature dependence of ion association was dominated by concentration effects. There appears to be a maximum in the fraction of “free” ions at a LiCF₃SO₃ concentration of 0.4 mol dm^-3, preceded by a minimum at approximately 0.2 mol dm^-3, consistent with the molar conductivity behavior previously observed in these electrolytes.

Ionic conductivity studies of polymeric electrolytes containing lithium salt with plasticizer

New plasticized polymer electrolytes were synthesized based on poly ethylene oxide (PEO), Poly (N,N-dimethylamino-ethyl-methacrylate) (PDMAEMA), LiN(CF₃SO₂)₂ (LITFSI) as the salt and tetraethylene glycol dimethyl ether(tetraglyme) and EC + PC as plasticizers. The preparation and characterization of the polymer electrolytes were investigated as a function of temperature and various concentrations of LITFSI. Impedance spectroscopy and differential scanning calorimeter (DSC) were used to characterize the effects of various temperature, lithium salt concentration and two plasticizers on conductivity. The complex of PDMAEMA/PEO/LiTFSI/tetraglyme (S2) exhibits higher conductivity (4.74 × 10⁻⁴ S cm⁻¹at 25 °C) than PDMAEMA/PEO/LiTFSI/EC + PC (S1).

Ion clustering in molecular dynamics simulations of sodium iodide solutions

Model systems of sodium iodide dissolved in dimethyl ether or 1,2-dimethoxyethane (glyme) were studied in order to investigate the structural and dynamic properties of ionic solutions in small and polymeric ethers. Full molecular dynamics simulations were performed at a range of different salt concentrations. An algorithm was designed which assigns ions to clusters and then calculates all the terms which contribute to ionic conductivity. In dilute solutions, free ions are the most common ionic species, followed by ion pairs. As the concentration increases, pairs become the most common species, with significant concentrations of clusters with 3 through 6 ions. Changing the solvent from dimethyl ether to glyme significantly decreases the ion clustering due to the chelate effect in which the two oxygens on a solvent stabilize an associated cation. The conductivity in stable systems is shown to be primarily the result of the movement of free ions and the relative movement of ions within neutral pairs. The Nernst-Einstein relation, commonly used in the discussion of polymer electrolytes, is shown to be inadequate to quantitatively describe conductivity in the model systems.

Poly methacrylate-plasticiser-salt blends as solid polymer electrolytes

Methoxy-ethylene glycol methacrylates, CH₂=CMeCOO(CH₂CH₂O)_nMe (n = 1, 2, 3), ethoxy-triethylene glycol methacrylate, CH₂=CMeCOO(CH₂CH₂O)₃Et, and N,N-dimethylaminoethyl methacrylate, CH₂=CMeCOOCH₂CH₂NMe₂, were used to synthesise the corresponding polymers. Conductivities of these polymers complexed with lithium perchlorate were investigated. Tetraethylene glycol dimethyl ether was used as plasticiser to increase the conductivity of the materials. A conductivity of 10⁻⁵ S cm⁻¹ was obtained at room temperature for the plasticised polymer samples. Effects of polymer structure, plasticiser, salt concentration and temperature on conductivity and glass transition temperature of the polymer electrolytes are discussed.

Mechanical properties of polyether-plasticiser-salt systems as polymer electrolytes

The mechanical properties of urethane crosslinked poly(ethylene oxide-co-propylene oxide) glyceryl ether-plasticiser (tetraethylene glycol dimethyl ether, or methylformamide)-salt (LiClO₄)-based polymer electrolytes have been studied. It was found that, with increasing concentration of salt, the elastic modulus and tensile strength of the materials unexpectedly decrease. This is interpreted in terms of a predominance of intramolecular coordination of the Li⁺ ions by the polymer.

Effect of zwitterions on electrochemical properties of oligoether-based electrolytes

Solid polymer electrolytes show great potential in electrochemical devices. Poly(ethylene oxide) (PEO) has been studied as a matrix for solid polymer electrolytes because it has relatively high ionic conductivity. In order to investigate the effect of zwitterions on the electrochemical properties of poly(ethylene glycol) dimethyl ether (G5)/lithium bis(fluorosulfonyl) amide (LiFSA) electrolytes, a liquid zwitterion (ImZ2) was added to the G5-based electrolytes. In this study, G5, which is a small oligomer, was used as a model compound for PEO matrices. The thermal properties, ionic conductivity, and electrochemical stability of the electrolytes with ImZ2 were evaluated. The thermal stabilities of all the G5-based electrolytes with ImZ2 were above 150 °C, and the ionic conductivity values were in the range of 0.8–3.0 mS cm−1 at room temperature. When the electrolytes contained less than 5.5 wt% ImZ2, the ionic conductivity values were almost the same as that of the electrolyte without ImZ2. The electrochemical properties were improved with the incorporation of ImZ2. The anodic limit of the electrolyte with 5.5 wt% ImZ2 was 5.3 V vs. Li/Li+, which was over 1 V higher than that of G5/LiFSA.

Optical and structural properties of PEO-like plasma polymers

This paper deals with the study of optical, structural and biocompatible properties of PEO-like plasma polymerized films resulting from RF excited diethylene glycol dimethyl ether (CH3O(CH2CH2O)(2)CH3 diglyme) glow discharges. The study was carried out using visible-ultraviolet and FTIR spectroscopies and contact angle measurements. FTIR spectra of plasma polymerized diglyme showed a stronger presence of ethylene glycol groups in film structure for lower RF power levels. The contact angle measurements for water revealed an increasing from 30degrees to 62,5degrees when the RF power was varied from 2 to 45 W, indicating the decreasing of the hydrophilic character of diglyme films with the increasing of RF power. This trend is in agreement with FTIR results. The data from visible-ultraviolet reflectance and transmittance spectra revealed alterations on optical properties of plasma polymerized diglyme films. The film's optical gap varied from 3.8 to 3 eV for RF power running from 5 to 45 W.

Polyurethane coating with thin polymer films produced by plasma polymerization of diglyme

Aqueous-based polyurethane dispersions have been widely utilized as lubricants in textile, shoes, automotive, biomaterial and many other industries because they are less aggressive to surrounding environment. In this work thin films with different thickness were deposited on biocompatible polyurethane by plasma polymerization process using diethylene glycol dimethyl ether (Diglyme) as monomer. Molecular structure of the films was analyzed by Fourier Transform Infrared spectroscopy. The spectra exhibited absorption bands of O-H (3500-3200cm(-1)), C-H (3000-2900cm(-1)), C=O (1730-1650cm(-1)), C-O and C-O-C bonds at 1200-1600cm(-1). The samples wettability was evaluated by measurements of contact angle using different liquids such as water, glycerol, poly-ethane and CMC. The polyurethane surface showed hydrophilic behavior after diglyme plasma-deposition with contact angle dropping from 85(0) to 22(0). Scanning Electron Microscopy revealed that diglyme films covered uniformly the polyurethane surfaces ensuring to it a biocompatible characteristic.

Nitro derivatives and other constituents of Aristolochia melastoma

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Plasma-deposition of Ag-containing polyethyleneoxide-like coatings

Ag-containing polyethyleneoxide (FEO)-like thin films have been deposited in Radio Frequency Glow Discharges fed with vapors of diethyleneglycol-dimethyl-ether and argon. Proper experimental conditions have been utilized in order to fragment the monomer in the glow and, at the same time, sputter Ag from the silver RF cathode of the reactor, in a way that polyethyleneoxide(PEO)-like coatings with embedded Ag clusters have been deposited at the ground electrode. The composition of the coatings has been investigated by means of different techniques; the plasma process has been investigated by means of Actinometric Optical Emission Spectroscopy. A correlation has been found between the amount of silver embedded in the coatings and that sputtered in the discharge, monitored by actinometry, that could eventually be utilized to control in situ the deposition process.

Constituintes micromoleculares de Aristolochia melastoma Manso: compostos nitrados

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Investigação eletroquímica e aplicação de eletrodos de carbono vítreo modificados por filmes de poli-L-lisina na determinação de antioxidantes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)