914 resultados para Tert-butyl hydroperoxide


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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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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 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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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.

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Asymmetric MarcusHush (AMH) theory is applied for the first time in ionic solvents to model the voltammetric reduction of oxygen in 1-butyl-1-methylpyrrolidinium bis-(trifluoromethylsulfonyl)-imide and of 2-nitrotoluene (2-NT), nitrocyclopentane (NCP), and 1-nitro-butane (BuN) in trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate on a gold microdisc electrode. An asymmetry parameter, gamma, was estimated for all systems as -0.4 for the reduction of oxygen and -0.05, 0.25, and 0 +/- 0.05 for the reductions of 2-NT, NCP, and BuN, respectively, which suggests equal force constants of reactants and products in the case of 2-NT and BuN and unequal force constants for oxygen and NCP where the force constants of the oxidized species are greater than the reduced species in the case of oxygen and less than the reduced species in the case of NCP. Previously measured values for a, the Butler-Volmer transfer coefficient, reflect this in each case. Where appreciable asymmetry occurs, AMH theory was seen to parametrize the experimental data better than either Butler-Volmer or symmetric Marcus-Hush theory, allowing additionally the extraction of reorganization energy. This is the first study to provide key physical insights into electrochemical systems in room-temperature ionic liquids using AMH theory, allowing elucidation of the reorganization energies and the relative force constants of the reactants and products in each reaction.

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Two ionic liquids, 1-ethylpyridinium docusate (IL1) and tri-n-butyl(2-hydroxyethyl)phosphonium docusate (IL2), were designed and synthesized with the explicit intention of imparting a combination of plasticization and antimicrobial efficacy when incorporated into medical grade poly(vinyl chloride)s (PVCs). The glass transition (T-g) of PVC can be reduced by >20 degrees C on addition of 15 wt% IL2. Both IL1 and IL2 leached to varying extents from the base PVC resins rendering the surface of the PVCs hydrophilic. The antimicrobial activity of both ILs is related to the presence and concentration of both cationic and anionic component of the ILs leached from the PVC and inversely proportional to the extent of PVC gelation. Blends of the PVCs with IL1 displayed antibacterial activity against almost all Gram-positive bacteria tested, including coagulase-negative Staphylococci (CoNS) and methicillin-resistant Staphylococcus aureus (MRSA), but not with IL2 at low concentration in contrast to our previous study when high concentrations of IL2 were used. The more hydrophilic IL1 when added to PVC retards biofilm formation.

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The adsorption of water and deuterium oxide on TiO2 surfaces was investigated in the dark as well as under UV(A) irradiation using in situ ATR-FTIR spectroscopy under oxygen and oxygen free conditions. Adsorption of H2O-D2O mixtures revealed an isotopic exchange reaction occurring onto the surface of TiO2 in the dark. Under UV(A) irradiation, the amount of both OH and OD groups was found to be increased by the presence of molecular oxygen. Furthermore, the photocatalytic formation of hydroperoxide under oxygenated condition has been recorded utilizing Attenuated Total Reflection Fourier Transformed Infrared (ATR-FTIR) spectroscopy which appeared as new band at 3483 cm-1. Different possible mechanisms are discussed in terms of the source of hydroxyl groups formed and/or hydration water on the TiO2 surface for the photocatalytic reaction and photoinduced hydrophilicity.

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In this work, 1-hexene was extracted from its mixtures with n-hexane in varying ratios using a task specific ionic liquid. Herein, the ionic liquid (IL) 1-butyl-3-methylimidazolium nitrate, [BMIM][NO3], was used and examined with and without the addition of a metal salt. The impact of water on both selectivity and distribution coefficient was also tested. Four potential metal salts were investigated, the results of which demonstrate that the dissolution of transition-metal salts in the IL improves the separation of 1-hexene from n-hexane through metal-olefin complexation. Additionally, the presence of water in IL solutions containing metal salt enhances this selectivity. Finally, UNIFAC was used to correlate the experimental LLE data with good accuracy.

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Heterocyclic chalcogenones were prepd. by reaction of S, Se, or Te with ionic liqs. or salts [I; Ra = (substituted) alkyl, cycloalkyl, aryl, aralkyl, alkylaryl; Q = (unsatd.) (substituted) linker to form a ring of 5-10 members; X- = anion selected from conjugate bases of HX having a pKa value of >2.5]. Thus, 1-butyl-3-methylimidazolium acetate was heated with stoichiometric S at 75° for 48 h to give 1-butyl-3-methylimidazole-2-thione. [on SciFinder(R)]

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The process involves encapsulation or immobilization of the active solid substance in a cellulose framework by regenerating cellulose dissolved in an ionic liq. solvent in a regenerating soln. The active substance can be initially present in the ionic liq. or in the regenerating solvent either as a soln. or dispersion. The invention is applicable to mol. encapsulation and to entrapping of larger particles including enzymes, nanoparticles and macroscopic components, and to the formation of bulk materials with a wide range of morphol. forms. Thus, carbamoylmethylphosphine oxide (I) encapsulated in a cellulose matrix was realized by adding I to a 10% soln. of cellulose in 1-butyl-3-methylimidazolium chloride (ionic liq.) under vigorous stirring and then removing the ionic liq. with water. [on SciFinder(R)]