190 resultados para butyl radicals


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OBJECTIVE: To assess the effectiveness of n-butyl-2-cyanoacrylate glue compared with microsuturing technique in peripheral nerve reanastomosis in rats.

STUDY DESIGN: Fourteen young adult white rats were used. Bilateral sciatic neurotomies were performed in 12 of them and then reanastomosed with 3 epineural microsutures in the right side (study group G1) and with n-butyl-2-cyanoacrylate glue in the left side (study group G2). On the remaining 2 rats (control group G3), sham surgery was done on both sides. Biopsies were harvested 12 weeks after surgery and examined under light microscope using Osmic acid stains. The number of nerve fibers was counted in the distal and proximal nerve segments, and the results were analyzed and compared in all groups.

RESULTS: Adequate regeneration with no anastomotic ruptures was seen 12 weeks after surgery in G1 and G2. The histomorphometric assessment showed no statistically significant difference (P = .960) in the neurotization index of G1 (89.01%) compared with G2 (88.97%). There was a significant (P = .001) reduction in the mean number of axon counts distal to the repair in G1 (271.3) and G2 (272.8) compared with that of the proximal segments of each study group (304.6 and 303, respectively, as well as to that of G3 (348.5).

CONCLUSION: Both n-butyl-2-cyanoacrylate adhesive and 3-microsuture techniques showed comparable neurotization indices and were equally adequate to stabilize the nerve during regeneration period.

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The absolute yield of hydroxyl radicals per unit of deposited X-ray energy is determined for the first time for irradiated aqueous solutions containing metal nanoparticles based on a “reference” protocol. Measurements are made as a function of dose rate and nanoparticle concentration. Possible mechanisms for hydroxyl radical production are considered in turn: energy deposition in the nanoparticles followed by its transport into the surrounding environment is unable to account for observed yield whereas energy deposition in the water followed by a catalytic-like reaction at the water-nanoparticle interface can account for the total yield and its dependence on dose rate and nanoparticle concentration. This finding is important because current models used to account for nanoparticle enhancement to radiobiological damage only consider the primary interaction with the nanoparticle, not with the surrounding media. Nothing about the new mechanism appears to be specific to gold, the main requirements being the formation of a structured water layer in the vicinity of the nanoparticle possibly through the interaction of its charge and the water dipoles. The massive hydroxyl radical production is relevant to a number of application fields, particularly nanomedicine since the hydroxyl radical is responsible for the majority of radiation-induced DNA damage.

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Herein, we present the formulation and the characterization of novel adiponitrile-based electrolytes as a function of the salt structure, concentration, and temperature for supercapacitor applications using activated carbon based electrode material. To drive this study two salts were selected, namely, the tetraethylammonium tetrafluoroborate and the 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide. Prior to determination of their electrochemical performance, formulated electrolytes were first characterized to quantify their thermal, volumetric, and transport properties as a function of temperature and composition. Then, cyclic voltammetry and electrochemical impedance spectroscopy techniques were used to investigate their electrochemical properties as electrolyte for supercapacitor applications in comparison with those reported for the currently used model electrolyte based on the dissolution of 1 mol·dm–3 of tetraethylammonium tetrafluoroborate in acetonitrile. Surprisingly, excellent electrochemical performances were observed by testing adiponitrile-based electrolytes, especially those containing the 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide room-temperature molten salt. Differences observed on electrochemical performances between the selected adiponitrile electrolytes based on high-temperature (tetraethylammonium tetrafluoroborate) and the room-temperature (1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide) molten salts are mainly driven by the salt solubility in adiponitrile, as well as by the charge and the structure of each involved species. Furthermore, in comparison with classical electrolytes, the selected adiponitrile +1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide solution exhibits almost similar specific capacitances and lower equivalent serial resistance. These results demonstrate in fact that the adiponitrile +1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide mixture can be used for the formulation of safer electrolytes presenting a very low vapor pressure even at high temperatures to design acetonitrile-free supercapacitor devices with comparable performances.

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In this work we examine, for the first time, the molar conductivity behavior of the deeply supercooled room temperature ionic liquid [C4mim][NTf2] in the temperature, pressure and volume thermodynamic space in terms of density scaling (TVγ)−1 combined with the equation of state (EOS). The exponent γσ determined from the Avramov model analysis is compared with the coefficient obtained from the viscosity studies carried out at moderate temperatures. Therefore, the experimental results presented herein provide the answer to the long-standing question regarding the validity of thermodynamic scaling of ionic liquids over a wide temperature range, i.e. from the normal liquid state to the glass transition point. Finally, we investigate the relationship between the dynamic and thermodynamic properties of [C4mim][NTf2] represented by scaling exponent γ and Grüneisen constant γG, respectively.

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This work comprises the photoactivity assessment of transparent sol–gel TiO2 coatings of various thickness using two test systems. The initial rates of both photocatalytic reactions, namely the oxidative bleaching of Acid Orange 7 (AO7) and the reductive bleaching of 2,6-dichlorindophenol (DCIP) increase linearly with increasing titania film thickness as well as with increasing absorbed light flux. The latter work revealed quantum yields (QY) of 0.19% and 92% for the AO7 and DCIP test system, respectively. The low QY for the AO7 oxidation is due to the combination of a slow irreversible reduction of oxygen and also for the oxidation of AO7, thus favouring the high efficiency for electron–hole recombination that is typical for aqueous organic pollutants. In contrast, the very high QY for the photocatalysed reduction of DCIP is due to the presence of a vast excess of glycerol which traps the photogenerated holes efficiently and so allow time for the slower reduction of dye to take place. Furthermore, the oxidation of glycerol results in the generation of highly reducing R-hydroxyalkyl radicals that are able to also reduce DCIP. As a consequence of this ‘current doubling’ effect, the observed QY (92%) is much higher than the apparent theoretical value of 50%.

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The effect of a radio-frequency driven, microscale non thermal atmospheric pressure plasma jet operated in helium with vol. 0.3% molecular oxygen gas admixture, on PC-3 prostate cancer cells has been investigated. The viability of cells exposed to the plasma was found to decrease with increasing plasma exposure time, with apoptosis through caspase and PARP cleavage being observed. High concentrations of nitrite and nitrate were detected in growth media exposed to the plasma and were found to increase in a time dependent manner post exposure. This indicates a slow release of reactive nitrogen species into the growth media, which is likely to influence cellular response to plasma exposure.

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Highly reactive radicals play an important role in high-temperature gasification processes. However, the effect of radicals on gasification has not been systematically investigated. In the present study, the formation of carbon-radical precursors using atomic radicals such as OH, O, and H and molecules such as H2 and O2 was characterized, and the effect of the precursors on the adsorption step of steam char gasification was studied using quantum chemistry methods. The results revealed that the radicals can be chemisorbed exothermically on char active sites, and the following order of reactivity was observed: O > H2 > H > OH > O 2. Moreover, hydrogen bonds are formed between steam molecules and carbon-radical complexes. Steam molecule adsorption onto carbon-O and carbon-OH complexes is easier than adsorption onto clean carbon surfaces. Alternatively, adsorption on carbon-O2, carbon-H2, and carbon-H complexes is at the same level with that of clean carbon surfaces; thus, OH and O radicals accelerate the physical adsorption of steam onto the char surface, H radical and O2 and H2 molecules do not have a significant effect on adsorption. © 2010 American Chemical Society.

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This work provides a first-time-study of Azepanium-based ionic liquids (ILs) as electrolyte components for electrochemical double layer capacitors (EDLCs). Herein, two Azepanium-based ILs, namely N-methyl, N-butyl-azepanium bis(trifluoromethanesulfonyl)imide (Azp(14)TFSI) and N-methyl, N-hexyl-azepanium bis(trifluoromethanesulfonyl)imide (Azp(16)TFSI) were compared with the established IL N-butyl, N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr(14)TFSI) in terms of viscosity, conductivity, thermal stability and electrochemical behavior in EDLC systems. The ILs' operative potentials were found to be comparable, leading to operative voltages up to 3.5 V without significant electrolyte degradation. 

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Herein, the N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)amide and the N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)amide room temperature ionic liquids, combined with the lithium bis(trifluoromethanesulfonyl)amide salt, are investigated as electrolytes for Li/LiNi1/3Mn1/3Co1/3O2 (Li/NMC) batteries. To conduct this study, volumetric properties, ionic conductivity and viscosity of the pure ionic liquids and selected electrolytes were firstly determined as a function of temperature and composition in solution. These data were then compared with those measured in the case of the standard alkyl carbonate-based electrolyte: e.g. the EC/PC/3DMC + 1 mol·L−1 LiPF6. The compatibility of the selected electrolytes with the lithium electrode was then investigated by following the evolution of Li/electrolyte interfaces through impedance measurements. Interestingly, the impedances of the investigated Li/electrolyte interfaces were found to be more than three times lower than that measured using the standard electrolyte. Finally, electrochemical performances of the ionic liquid-based electrolytes were investigated using galvanostatic charge and discharge and cyclic voltammetry of each Li/NMC cell. Using these electrolytes, each tested Li cell reaches up to 145 mA·h·g−1 at C/10 and 110 mA·h·g−1 at C with a coulombic efficiency close to 100 %.

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This work provides a study of mixtures of the azepanium-based ionic liquid (IL) N-methyl, N-butyl-azepanium bis[(trifluoromethane) sulfonyl]imide (Azp14TFSI) and propylene carbonate (PC) as electrolyte components in electrochemical double layer capacitors (EDLCs). The considered mixtures' properties were then compared to the properties of mixtures of N-butyl, N-methylpyrrolidinium bis[(trifluoromethane) sulfonyl]imide (Pyr14TFSI) and PC in terms of viscosity, conductivity and electrochemical behavior. The mixtures' operative potentials were found to be comparable to each other, leading to operative voltages as high as 3.5 V, while retaining the low viscosities and high conductivities of PC based EDLC electrolytes.

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TiO2 photocatalysis has demonstrated efficacy as a treatment process for water contaminated with chemical pollutants. When exposed to UVA light TiO2 also demonstrates an effective bactericidal activity. The mechanism of this process has been reported to involve attack by valence band generated hydroxyl radicals. In this study when three common bacterial pathogens, Escherichia coli, Salmonella enterica serovar Enteritidis and Pseudomonas aeruginosa, were exposed to TiO2 and UVA light a substantial decrease in bacterial numbers was observed. Control experiments in which all three pathogens were exposed to UVA light only resulted in a similar reduction in bacterial numbers. Moreover, exposure to UVA light alone resulted in the production of a smaller than average colony phenotype among the surviving bacteria, for all three pathogens examined, a finding which was not observed following treatment with UVA and TiO2. Small slow growing colonies have been described for several pathogenic bacteria and are referred to as small colony variants. Several studies have demonstrated an association between small colony variants and persistent, recurrent and antibiotic resistant infections. We propose that the production of small colony variants of pathogenic bacteria following UVA treatment of drinking water may represent a health hazard. As these small colony variants were not observed with the UVA/TiO2 system this potential hazard is not a risk when using this technology. It would also appear that the bactericidal mechanism is different with the UVA/TiO2 process compared to when UVA light is used alone.

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Herein, we report the densities and speeds of sound in binary mixtures of three hydrophobic and one hydrophilic ionic liquids: 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [C4mim][NTf2], 1-butyl-1-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide, [C4mpyr][NTf2], 1-propyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [C3mim][NTf2] and 1-ethyl-3-methylimidazolium thiocyanate, [C2mim][SCN], with water at 298.15 K and 0.1 MPa. The concentration range of water, which encompassed relatively small values well below the saturation point, is often regarded as an impurity for hydrophobic ionic liquids. On the basis of experimental results the molar volume, adiabatic molar compressibility, partial molar volume and apparent molar volume, as well as, partial molar and apparent molar isentropic compressibility properties were then calculated. Interesting results are obtained using the solutions based on the hydrophilic [C2mim][SCN], since these mixtures are characterized by relatively low density and high values of speed of sound. Furthermore, the partial molar volumes and partial molar adiabatic compressibilities of water in solution with [C2mim][SCN] are the lowest among the investigated in mixtures with ionic liquids. However, in the case of the hydrophobic ionic liquid solutions, only small differences are observed for molar adiabatic compressibilities with the change of the cation structure, i.e. for water + [C4mim][NTf2] or + [C4mpyr][NTf2]. A more pronounced difference has been observed for the partial molar compressibility of water in solutions with these two ionic liquids.

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Metallo-azomethine ylides, generated from imines by the action of amine bases in combination with LiBr or AgOAc, undergo cycloaddition with both 1R, 2S, 5R- and 1S, 2R, 5S-menthyl acrylate at room temperature to give homochiral pyrrolidines in excellent yield. The stronger the base the faster the cycloaddition and the greater the yield with: 2-t-butyl-1,1,3,3-tetramethylguanidine > DBU > NEt(3) X-Ray crystal structures of representative cycloadducts establish that the absolute configuration of the newly established pyrrolidine stereocentres is independent of the metal salt and the size of the pyrrolidineC(2)-substituent for a series of aryl and aliphatic imines.

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A wide range of room temperature ionic liquids based on the 3-methylpiperdinium cation core were produced from 3-methylpiperidine, which is a derivative of DYTEK® A amine. First, reaction with 1-bromoalkanes or 1-bromoalkoxyalkanes generated the corresponding tertiary amines (Rmβpip, R = alkyl or alkoxyalkyl); further quaternisation reactions with the appropriate methylating agents yielded the quaternary [Rmmβpip]X salts (X(-) = I(-), [CF3CO2](-) or [OTf](-); Tf = -SO2CF3), and [Rmmβpip][NTf2] were prepared by anion metathesis from the corresponding iodides. All [NTf2](-) salts are liquids at room temperature. [Rmmβpip]X (X(-) = I(-), [CF3CO2](-) or [OTf](-)) are low-melting solids when R = alkyl, but room temperature liquids upon introduction of ether functionalities on R. Neither of the 3-methylpiperdinium ionic liquids showed any signs of crystallisation, even well below 0 °C. Some related non-C-substituted piperidinium and pyrrolidinium analogues were prepared and studied for comparison. Crystal structures of 1-hexyl-1,3-dimethylpiperidinium tetraphenylborate, 1-butyl-3-methylpiperidinium bromide, 1-(2-methoxyethyl)-1-methylpiperidinium chloride and 1-(2-methoxyethyl)-1-methylpyrrolidinium bromide are reported. Extensive structural and physical data are collected and compared to literature data, with special emphasis on the systematic study of the cation ring size and/or asymmetry effects on density, viscosity and ionic conductivity, allowing general trends to be outlined. Cyclic voltammetry shows that 3-methylpiperidinium ionic liquids, similarly to azepanium, piperidinium or pyrrolidinium counterparts, are extremely electrochemically stable; the portfolio of useful alternatives for safe and high-performing electrolytes is thus greatly extended.