Electrocatalytic hydrogenation of cyclohexanone: Simple dynamic cell design

The electrocatalytic hydrogenation of cyclohexanone has been investigated with catalytic powder particles made of metal nanoaggregates deposited on a nonconductive material such as activated carbon and alumina. The catalytic powder particles were suspended in the solution under vigorous stirring conditions. The brief contact of the powder particles with a porous carbon cathode was sufficient to form adsorbed hydrogen on the metallic nanoaggregates through water electrolysis and initiate the electrohydrogenation process. It is demonstrated that the key parameters of the electrohydrogenation process are both the nature of the metallic nanoaggregates and the nature of the non-conductive material. The hydrodynamics of the solution under vigorous stirring conditions have also been studied for the particular cell used in the present study.     

γ-Butyrolactone-ethylene carbonate based electrolytes for lithium-ion batteries

-Butyrolactone-ethylene carbonate (BL-EC) mixtures have been investigated as electrolytes for Li-ion batteries using LiPF₆ and LiBF₄ as lithium salt. The thermal stability of the electrolytes in a large range of temperatures (–90 °C to 40 °C) have been studied by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). From the results of these experiments, the phase diagram of the BL-EC system has been determined. It is characterised by a eutectic point at –56.3 °C and a molar fraction in EC: x _EC = 0.1. A metastable compound has been demonstrated below –90 °C at x _EC = 0.4. Conductivity measurements of BL-EC solutions, in the presence of LiPF₆ and LiBF₄, indicate that LiPF₆ in the eutectic mixture is the most conducting electrolyte in the range of temperatures investigated (–30 °C to room temperature). Nevertheless, at low temperature, LiBF₄ based electrolytes compete well with LiPF₆, especially when the amount of EC in the mixture is as high as x _EC = 0.5. Moreover, recrystallisation of the salt below –20 °C is avoided when LiBF₄ is used as salt. A large increase in viscosity of the solvent mixture is observed when a salt is added, but the increase is lower for LiBF₄ than LiPF₆. When EC is added to BL at constant salt concentration (1 M), the conductivity of LiPF₆ solutions decreases more rapidly than LiBF₄ solutions. This has been attributed, at least partially, to the dissociating power of EC. The electrochemical windows of BL-EC (equimolar) mixtures in the presence of LiPF₆ and LiBF₄ are comparable but it is shown that the solvents oxidation rate at high potentials is lower when LiBF₄ is used.     

Electrooxidation of methanol at platinum–ruthenium catalysts prepared from colloidal precursors: Atomic composition and temperature effects

The electrocatalytic oxidation of methanol was investigated on PtRu electrodes of different atomic compositions at several temperatures (from 25 to 110 °C). Very active catalyst nanoparticles supported on active carbon (Vulcan XC 72) were obtained using the colloidal synthesis developed by Bönnemann et al. [11], allowing easy variation of the atomic composition. These electrocatalysts were characterized by TEM, EDX and XRD; results indicate that they consist of platinum nanoparticles decorated by ruthenium. Methanol oxidation was studied as a function of composition, temperature and methanol concentration. Two effects were investigated: the effect of the working temperature and the effect of the atomic composition. It appeared that for lower methanol electrooxidation overvoltages, the best catalysts are ruthenium-rich, whereas at higher overvoltages the best one is the Pt + Ru (80:20)/C composition, irrespective of the working temperature, either in half-cell or in a single DMFC.     

Fourier-transform infrared spectra of fatty acid salts—Kinetics of high-oleic sunflower oil saponification

Sodium, lithium, and calcium soaps obtained by saponification of high-oleic sunflower oil were studied by Fourier-transform infrared spectroscopy. Spectra of crude mixtures containing soap, glycerin, residual alkali, and triacylglycerols were compared to those of pure soaps obtained from fatty acids. The infrared spectra of crude soaps showed the same characteristic bands as pure ones. The absorption bands of asymmetric (ω₂) and symmetric (ω₁) stretching vibrations of the carboxylate group indicated that the metal-oxygen bonds of these soaps had an ionic character whose strength differed from one cationic counterion to another. Once the characteristic absorption bands of the soaps were assigned, a kinetics study of saponification was performed. Saponification by sodium, anhydrous lithium, and calcium hydroxides was an autocatalytic reaction, characterized by an S-shaped kinetics curve, whereas saponification by aqueous lithium hydroxide was stoichiometric. The structure of the metal-oxygen bond played a role in the kinetic mechanisms.     

Simulation of multistage extraction of antioxidants from Chilean hazelnut (<Emphasis Type="Italic">Gevuina avellana</Emphasis>) hulls

The objective of this study was to analyze the factors affecting the ethanol extraction of Chilean hazelnut (Gevuina avellana) hulls to obtain antioxidant compounds. The effects of temperature on the kinetics of polyphenolics extraction and on the antioxidant activities of the extracts were assessed. The radical-scavenging activities of the extracts were comparable with that of BHA when used at the same concentration. The optimal temperature for the antioxidant activities of the extracts was 40°C. A four-stage cross-flow extraction was carried out and a four-stage countercurrent extraction was simulated, where each stage lasted 30 min. Best results were obtained with countercurrent extraction, which produced an extract that showed 94.4% α,α-diphenyl-β-picrylhydazyl radical inhibition, compared with 86.2% obtained in the first stage of cross-flow extraction and 92.62% in a batch extraction that lasted 100 h. UV-vis and NIR spectra of extracts from cross-flow and from the simulated countercurrent extraction revealed that the composition of extracts varied along the stages and was affected by the operational strategy.     

Natural estolides produced by <Emphasis Type="Italic">Pseudomonas</Emphasis> sp. 42A2 grown on oleic acid: Production and characterization

Estolides are a group of FA polyesters resulting from ester bond formation between a hydroxyl or olefinic group of one FA and the terminal carboxyl group of a second FA. These products are commonly found in trace amounts, forming tetraglycerides in several oil seed plants, and have been produced by acid clay and enzymatic catalysis in vitro. In this study, natural estolides produced by a bacterial culture are presented for the first time. Pseudomonas sp. 42A2 produced (E)-10-hydroxy-8-octadecenoic acid and (E)-7,10-dihydroxy-8-octadecenoic acid when grown on oleic acid. It is suggested that these FA were polymerized in culture by a lipase produced by the bacterial strain, resulting in a mixture of estolides. These compounds amounted to 3.8 g/L after 72 h of incubation. LC-MS analysis indicated that the types of estolides formed were dimers (m/z 560–610), trimers (m/z 845–906), tetramers (m/z 1122–1202), pentamers (m/z 1328–1424), and hexamers (m/z 1554–1788), with a relative abundance of 27.5, 19.4, 15, 9.7, and 11%, respectively. This is the first report in which hexamers were detected in a bacterial culture.     

Chemical and electrochemical considerations on the removal process of hexavalent chromium from aqueous media

Two methods were used to remove Cr(VI) from industrial wastewater. Although both are based in the same general reaction: 3Fe(II)_(aq) + Cr(VI)_(aq) ; 3Fe(III)_(aq) + Cr(III)_(aq) the way in which the required amount of Fe(II) is added to the wastewater is different for each method. In the chemical method, Fe(II)_(aq) is supplied by dissolving FeSO₄ · 7(H₂O)_(s) into the wastewater, while in the electrochemical process Fe(II)_(aq) ions are formed directly in solution by anodic dissolution of an steel electrode. After this reduction process, the resulting Cr(III)_(aq) and Fe(III)_(aq) ions are precipitated as insoluble hydroxide species, in both cases, changing the pH (i.e., adding Ca(OH)_2(s)). Based on the chemical and thermodynamic characteristics of the systems Cr(VI)–Cr(III)–H₂O–e^– and Fe(III)–Fe(II)–H₂O–e^– both processes were optimized. However we show that the electrochemical option, apart from providing a better form of control, generates significantly less sludge as compared with the chemical process. Furthermore, it is also shown that sludge ageing promotes the formation of soluble polynuclear species of Cr(III). Therefore, it is recommended to separate the chromium and iron-bearing phases once they are formed. We propose the optimum hydraulic conditions for the continuous reduction of Cr(VI) present in the aqueous media treated in a plug-flow reactor.     

Synthesis and catalytic application of Ni-supported carbon nanotubes for<Emphasis Type="Italic">n</Emphasis>-heptane cracking

Carbon nanotubes were synthesized by chemical vapor deposition and subsequently purified and oxidized by repeated treatment with nitric acid. After acid treatment the walls of carbon nanotubes became thinner and the surface area increased. The Ni-supported carbon nanotubes prepared by impregnation were applied to the cracking ofn- heptane to show an excellent activity. This indicates that the carbon nanotubes can serve as a good catalyst support with high dispersion of metallic components. The optimum Ni loading turned out to be about 5.2 mmol/g. The cracking product was found to contain mainly small hydrocarbons; thus the Ni-supported carbon nanotubes may be applied as a potential catalyst to the cracking of heavy hydrocarbons. A. M. Zhang was a visiting scholar at School of Chemical Engineering, Seoul National University. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Pharmacological modulation of fatty acid desaturation and of cholesterol biosynthesis in THP-1 cells

In THP-1 cells, simvastatin decreases, in a concentration-dependent manner, cholesterol synthesis and increases linoleic acid (LA) conversion to its long-chain derivatives, in particular to arachidonic acid, activating Δ6 and Δ5 fatty acid (FA) desaturases. The intermediates in cholesterol synthesis, mevalonate and geranylgeraniol, partially reverse the effects of simvastatin on the LA conversion. The aims of this work were to evaluate: (i) the correlation between cholesterol synthesis and desaturase activity and (ii) the possible involvement of protein isoprenylation in desaturase activity, assessed through pharmacological treatments. THP-1 cells were incubated with [1-¹⁴C]LA or with [1-¹⁴C]di-homo-γ-linolenic acid (DHGLA) and treated with simvastatin or with curcumin and nicardipine, inhibitors of desaturases. Curcumin was more active than nicardipine in inhibiting LA and DHGLA conversion: 20 μM curcumin, alone or with simvastatin, totally inhibited Δ6 and Δ5 desaturation steps; 10 μM nicardipine only partially inhibited the enzymes, being more active on Δ5 desaturase. Simvastatin treatment decreased the incorporation of acetate in cholesterol (−93.8%) and cholesterol esters (−70.2%), as expected. Curcumin and nicardipine also decreased cholesterol synthesis and potentiated simvastatin. Finally, the isoprenylation inhibitors (perillic acid and GGTI-286) neither affected the conversion of LA nor inhibited the Δ5 desaturase activity. In conclusion, our results indicate that there is no direct relationship between cholesterol synthesis and desaturase activity. In fact, simvastatin decreased cholesterol synthesis and enhanced LA conversion (mainly Δ5 desaturation), whereas curcumin and nicardipin decreased Δ5 desaturation, with a limited effect on cholesterol synthesis.     

Analysis of the solvent diffusion in glassy polymer films using a set inversion method

Within the framework of solvent diffusion in glassy polymers, this paper concerns an experimental study of toluene sorption and desorption in P(MMA/nBMA) copolymer films. Gravimetric experiments (quartz microbalance) are performed in a pressure and temperature controlled chamber. Coupling between solvent diffusion and viscoelastic relaxation is taken into account through the time-dependent solubility model, based on the Fick diffusion equation inside the film and a time variable boundary condition at the film/vapor interface. Viscoelastic relaxation is described by a first order model or by a stretched exponential. In the present paper, a special focus is given on the set inversion method used to analyze the data and to derive well-defined uncertainty intervals upon each determined quantity, taking all the uncertainties on the weight measurements into account. We find that the mutual diffusion coefficient strongly decreases in the glassy state, of about two orders of magnitude for a 0.05 decrease in the solvent weight fraction.