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31.
G. Gousset M. Touzeau M. Vialle C. M. Ferreira 《Plasma Chemistry and Plasma Processing》1989,9(2):189-206
A simple kinetic model predicting the concentration of oxygen atoms, metastable singlet molecules O2(a
1) and negative ions O — in the positive column of a DC glow discharge is developed. The calculated O and O2(a
1) concentrations are compared to previously reported measurements for pressuresp=0.2–2 Torr and discharge currentsI=10–80 mA. The electron density calculated from the continuity equationj=n
e
e v
d agrees well with experiment. The rate coefficients for electron impact processes used in the balance equations of O, O2(a
1), and O– were taken from the literature as a function of the reduced electric fieldE/N forE/N=40–80 Td. A reasonable agreement is obtained between the model and the experiment with a set of 10 reactions for the production and destruction of the above-mentioned species 相似文献
32.
Ana A. C. Pacheco Arnaldo F. da Silva Filho Kristoffer Kortsen Magnus W. D. Hanson-Heine Vincenzo Taresco Jonathan D. Hirst Muriel Lansalot Franck D'Agosto Steven M. Howdle 《Chemical science》2021,12(3):1016
Reversible addition–fragmentation chain transfer (RAFT) dispersion polymerisation of methyl methacrylate (MMA) is performed in supercritical carbon dioxide (scCO2) with 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) present as chain transfer agent (CTA) and surprisingly shows good control over PMMA molecular weight. Kinetic studies of the polymerisation in scCO2 also confirm these data. By contrast, only poor control of MMA polymerisation is obtained in toluene solution, as would be expected for this CTA which is better suited for acrylates. In this regard, we select a range of CTAs and use them to determine the parameters that must be considered for good control in dispersion polymerisation in scCO2. A thorough investigation of the nucleation stage during the dispersion polymerisation reveals an unexpected “in situ two-stage” mechanism that strongly determines how the CTA works. Finally, using a novel computational solvation model, we identify a correlation between polymerisation control and degree of solubility of the CTAs. All of this ultimately gives rise to a simple, elegant and counterintuitive guideline to select the best CTA for RAFT dispersion polymerisation in scCO2.RAFT dispersion polymerisation of methyl methacrylate is performed in scCO2 with 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) present as chain transfer agent (CTA) and surprisingly shows good control over PMMA molecular weight. 相似文献
33.
María?Belén?Sierra Marcela?A.?Morini Pablo?C.?SchulzEmail author María?Luján?Ferreira 《Colloid and polymer science》2005,283(9):1016-1024
Following the studies on the effect of double bonds in the surfactant hydrophobic tail on the formation of mixed surfactant aggregates, we studied the viscosity and density of the system Sodium 10-undecenoate (SUD)–decyltrimethylammonium bromide (DTAB)–water. We found that the partial molar volume (pmv) and intrinsic viscosity of both, micellised and unmicellised mixtures, are non-ideal, dependent on the mixture composition and related to structural changes in micelles. These phenomena are caused by the presence of the double bond at the distal extreme of the SUD molecule, which has some affinity with water by formation of hydrogen bonds. In particular, as far as we know, this is the first report on non-ideal behavior of the pmv in mixed micelles. 相似文献
34.
This work focuses on the optimization of the rheological behavior of suspensions considering different solvent compositions. The effects of methyl ethyl ketone (MEK)/ethanol (E) solvent mixtures on reaction sialon suspensions were investigated by measuring sedimentation behavior, adsorption of dispersant, and flow behavior. It was shown that both the flow behavior and the sedimentation behavior strongly depended on selection of solvent composition. Using 3 wt% KD1 as dispersant, well-dispersed colloidal suspensions could be obtained in MEK-rich solvents. The suspensions with 60 vol% MEK/40 vol% E as solvent could be fitted to the Bingham model with very low yield stress, while suspensions with pure MEK or ethanol-rich mixtures as solvent showed pseudo plastic behavior with relatively high yield stress values. A model was proposed to explain the different flow behaviors of suspensions considering the different configurations of dispersant at particles' surfaces. 相似文献
35.
M. Zampieri S. R. Lazaro C. A. Paskocimas A. G. Ferreira E. Longo J. A. Varela 《Journal of Sol-Gel Science and Technology》2006,37(1):9-17
Titanium citrate and lead and titanium citrate were prepared by polymeric precursor method in aqueous solution. This citrate
was analyzed by 1H, 13C NMR and gHMBC–NMR (Hetero-nuclear multiple-bond correlation) to investigate the formation of the citrate complexs and influence
of the Pb2+ ion in this complex. These complexs were characterized by interaction between Ti4+ ion and citric acid carboxyls. Quantum mechanic simulations in level ab initio were used to study the electronic structure and natural charges (NBO) to both the complexs. Such techniques indicated the
formation of an octahedral complex with an arrangement similar to Ti atom in the crystalline structure of the PbTiO3. A study using the technique FT-Raman made possible the confirmation of the interaction among the Ti4+ and Pb2+ ions with the citric acid carboxyls. 相似文献
36.
Rauter AP Martins A Borges C Ferreira J Jorge J Bronze MR Coelho AV Choi YH Verpoorte R 《Journal of chromatography. A》2005,1089(1-2):59-64
The anti-hyperglycemic flavonoid extract obtained from Genista tenera was first studied by liquid chromatography (LC)-diode array detection (DAD) which showed the presence of two major compounds. One of them was identified as genistein-7-O-glucoside. Luteolin-7-O-glucoside was detected as a minor constituent, while luteolin-7,3'-di-O-glucoside and rutin were found in trace amounts. LC-DAD-ESI-MS and NMR were used to confirm the structure of these compounds and allowed the elucidation of the structure of the unknown major compound, which is the flavonoid 5,7,4'-trihydroxyisoflavone-8-C-glucoside. 相似文献
37.
Hélder A. Santos Elisabete S. Ferreira Elisa J. Pereira Carlos M. Pereira Prof. Kyösti Kontturi Prof. Fernando Silva Prof. 《Chemphyschem》2007,8(10):1540-1547
The interaction between glucose oxidase (GOx) and phospholipid monolayers is studied at the 1,2-dichloroethane/water interface by electrochemical impedance spectroscopy. Electrochemical experiments show that the presence of GOx induces changes in the capacitance curves at both negative and positive potentials, which are successfully explained by a theoretical model based on the solution of the Poisson-Boltzmann equation. These changes are ascribed to a reduced partition coefficient of GOx and an increase of the permittivity of the lipid hydrocarbon domain. Our results show that the presence of lipid molecules enhances the adsorption of GOx molecules at the liquid/liquid interface. At low lipid concentrations, the adsorption of GOx is probably the first step preceding its penetration into the lipid monolayer. The experimental results indicate that GOx penetrates better and forms more stable monolayers for lipids with longer hydrophobic tails. At high GOx concentrations, the formation of multilayers is observed. The phenomenon described here is strongly dependent on 1) the GOx and lipid concentrations, 2) the nature of the lipid, and 3) the potential drop across the interface. 相似文献
38.
Desmond A. Young Daneel Ferreira David G. Roux 《Journal of polymer science. Part A, Polymer chemistry》1986,24(5):835-849
The structure and stereochemistry of four synthetic “angular” tetraflavanoid-condensed tannin derivatives are examined by high-resolution variable temperature 1H NMR. spectroscopy, and hence correlated with their dynamic behavior. Three “angular” oligomers exist as stable rotational isomers at ambient temperatures, thus contrasting with the mobility about their interflavanoid bonds of most natural profisetinidin “trimeric” and “tetrameric” homologs. A “linear” tetraflavanoid analog results from one of these regioselectively controlled condensations. 相似文献
39.
Julliane Diniz Yoneda Magaly Giro Albuquerque Ktia Zaccur Leal Peter R. Seidl Ralph A. Wheeler Scott E. Boesch Ricardo Bicca de Alencastro Maria Cecília B.V. de Souza Vitor F. Ferreira 《Journal of Molecular Structure》2006,778(1-3):97-103
Conformational analysis of nucleosides may have direct applications to the structure–activity relationship (SAR) studies and in the design of new drug candidates. Although conformational analysis may be accessed in many different ways, in this work it was performed using molecular dynamics (MD) simulation in order to study the dynamic behavior of a nucleoside derivative of 1,4-dihydro-4-oxoquinoline-3-carboxylic acid, synthesized by our group as a potential antiviral agent. The MD simulation was carried out during 10 ns in vacuum and in a box of water at two different temperatures (i.e., 300 and 600 K) using the AMBER force field. The in vacuum MD simulation results are in agreement with the crystallographic structure and with the DFT calculations of the nucleoside, revealing the anti conformer as the more stable one. The simulation in water, however, shows that both conformers may exist at 300 K, the temperature of the in vivo and in vitro assays, revealing that both the syn and anti conformers should be considered in a MD simulation study of the inhibitor–enzyme complex. Simulations are also in agreement with the NOE experiment, which shows that the anti conformer is the preferential one in DMSO-d6 solution at 298 K. 相似文献
40.
The steps of protochlorophyllide (Pchlide) photoreduction and subsequent chlorophyllide (Chlide) transformations which occur in the seconds to minutes time-scale were studied using a diode array spectrofluorometer in dark-grown barley leaves. The intensity of the excitation light was varied between 3 and 2,500 micromol m(-2) s(-1) and a series of fluorescence spectra were recorded at room temperature in the seconds and minutes time scales. In certain experiments, 77-K emission spectra were measured with the same equipment. The high quality of the spectra allowed us to run spectral resolution studies which proved the occurrence, at room temperature, of multiple Pchlide and Chlide forms found previously in 77-K spectra. The comparison of the 77-K and room-temperature spectra showed that the fluorescence yields of the nonphotoactive 633-nm Pchlide form and of the Chlide product emitting at 678 nm were temperature independent. The fluorescence intensity of aggregated NADPH-pigment-POR complexes (photoactive 656-nm Pchlide and 693-nm Chlide forms) were strongly increased at 77 K, while that of the NADP(+)-Chlide-POR (684-686-nm Chlide form) was much less affected by temperature. Information was obtained also about the dynamics of the transformation of pigment forms in the light at different photon densities. At low light intensities, the phototransformation of the 642-644-nm Pchlide form was faster than that of the 654-656-nm form. The relative amplitudes of Gaussian components related to different Chlide forms found after exposure to a constant amount of photons strongly depended on the light intensity used. Strong quenching of all Chlide components occurred upon prolonged exposure to high intensity light. These effects are discussed by considering the interconversion processes between different forms of the pigment-protein complexes, their relative fluorescence yields and energy migration processes. 相似文献