Authors:C. Robert Dennis, Jannie C. Swarts, and Dale W. Margerum
Protonation of copper(II)- and nickel(II) tetrapeptide complexes with bulky α-carbon substituents has been studied. The pKa-values for the second and terminal metal–N(peptide) bond formation have been determined spectrophotometrically. More than one deprotonated peptide nitrogen exists in a complex but the individual protonation steps for the different CuII–N(tetrapeptide) positions could not be accounted for by the variation of the hydrogen ion concentration in the same experiment, as the protonation of the different metal–N(tetrapeptide) positions takes place at different wavelengths. For the NiII-tetra-alanine complex, the proton transfer to the terminal and second deprotonated peptide nitrogens have been detected by varying the hydrogen ion at the same wavelength. The proton transfer to the terminal metal–N(tetrapeptide) of CuII- and NiII-tetrapeptide complexes show first order kinetics with respect to the hydrogen ion and the peptide complex concentration and proceed via an outside protonation pathway. The relatively high pKa values for the terminal deprotonated peptide nitrogen indicate the instability of this metal–N(peptide) bond due to strain in the chelate ring because of atom overcrowding of the bulky α-carbon substituents.
Authors:Oriana D'alessandro, Horacio J. Thomas, and Jorge E. Sambeth
A series of Mn–Ce(M) solids (M = K or Na), with molar ratios 100–0, 50–50 and 0–100 were prepared by co-precipitation of manganese and cerium nitrate from NaOH or KOH solutions at pH = 11. In addition, part of the solids precipitated with NaOH were dried and impregnated with a Cu2+ salt. The solids were characterized by XRD, Specific Surface Area, XPS and EDS. The characterization analyses show the formation of Mn mixed oxides with different oxidation states (Mn3+, Mn4+), for samples without Ce or Mn–Ce(M) 50–50. In the latter solid and in the one where there is no Mn, the formation of CeO2 (fluorite type) was detected. The samples were tested in the phenol removal in water at 100 °C and at atmospheric pressure with the aim to analyze the adsorbed species in the first stage of the adsorption-oxidation mechanisms. The results indicate, on the one hand, that [MnOx] is the active species in the process and that the most active solids are those that present (i) a higher concentration of OI, (ii) a higher amount of Mn4+ ions. DRIFT spectroscopy showed a possible mechanism of phenol adsorption on two sites, in the first one by H interaction of OH (phenol) with an OH of the catalyst and in the second, by the formation of a phenolate species between an O (OH phenol) and Mnn+.
Authors:István Szalai, Krisztina Kurin-Csörgei, and Miklós Orbán
The general model developed by Rábai for describing the dynamics of the two-substrate pH-oscillators was refined and shown that its appropriately formulated versions are suitable for the simulation of the dynamics both in the semi-batch and in the recently reported batch pH-oscillators as well.
Authors:Joanna Wiśniewska, Grzegorz Wrzeszcz, Stanisław Koter, and Tomasz Ligor
The kinetics of the oxidation of imipramine and opipramol using peroxydisulfate salts in the presence of a large excess of dibenzoazepine derivative (TCA) in acidic sulfate media was studied using UV–vis spectroscopy. The reaction between imipramine and S2O82− proceeds via the formation of two intermediates: a free organic radical and a dimeric dication. Further reaction of the intermediate dimeric dication leads to a positively charged radical dimer as one final product. Simultaneously, two other substituent cleavage degradation processes occur, leading to two dimeric derivatives. The first product, the positively charged radical dimer, and the next main product, a radical dimer without one alkyl substituent, were identified by EPR measurements. The measured kinetic trace is not first order and revealed a sigmoid shape with a characteristic induction time. The rate constants were determined by numerical analysis based on ordinary differential equations (ODEs). The reaction between opipramol and S2O82− proceeds by a two consecutive reaction scheme. The kinetics of the first degradation step were studied independently of the slower degradation reactions. Linear dependences, with zero intercept, of the pseudo-first-order rate constants (kobs) on [TCA] were determined for the first degradation process of opipramol.
Authors:M. R. Granados-Uribe, F. J. Lona-Ramírez, C. Pérez-Pérez, J. Barajas-Fernández, V. Rico Ramírez, and G. González-Alatorre
The nitrosation of 1,3-dialkylureas was carried out in the presence of carboxylic acids and halides in an aqueous perchloric medium. The aim of this work was to validate the proposed mechanism for the nitrosation of such substrates. In accordance with the rate limiting step of the proposed mechanism, the protonic transfer to the solvent, basic catalysis and an absence of catalysis by halides should be observed. The Br⊘nsted parameters were determined by basic general catalysis.
Authors:Xuan Tang, Yefei Nan, Fenglin Huang, and Xunli Zhang
The oscillatory behavior of the reaction of partial oxidation of methane has been investigated over metallic nickel surfaces. It was found that the chemical compositions and the reaction temperature within the reactor exhibited regular oscillations over a range of reactor temperatures between 710 and 930 °C with different feed gas compositions at flow rate ratios (Ar/CH4/O2) ranging from 30:29:1 to 30:12:18 cm3 min−1. When the reactor temperature increased, the oscillation frequency increased showing indicative correlations, while the amplitude decreased with the rise in system temperature. Varying feed gas composition resulted in complex changes in oscillatory waveforms, frequencies, amplitudes, and product selectivities. The oscillation was attributed to the cyclic reduction and oxidation of the nickel surface under the reaction conditions.
Authors:María A. Sánchez, Vanina A. Mazzieri, Mario R. Sad, and Carlos L. Pieck
The influence of the operating conditions and preparation methods of Ru–Sn–B/Al2O3 catalysts on the activity and selectivity for the hydrogenation of methyl oleate to oleyl alcohol was studied. It was found that catalysts prepared by incipient wetness (IW) are more active and selective than those prepared by co-impregnation. This better performance is possibly due to a lower level of residual chlorine. The experiences of hydrogenation of methyl oleate showed that activity increases as the reaction temperature increases while the selectivity to oleyl alcohol has a maximum value. This could be due to the higher activation energies for the hydrogenolysis of carboxymethyl groups than those found for C=C double bonds hydrogenation. The increase in operating pressure has a positive effect on the activity but it influences selectivity time patterns in a more complex way. Experiments carried out by varying methyl oleate/n-dodecane ratio show that the selectivity and conversion not depend on this parameter. A simple kinetic model is proposed.
A carbon-based solid acid catalyst was prepared by incomplete carbonization of H3PO4-impregnated pulp fibers followed by sulfonation. XRD, FT-IR, BET, TGA, and acid density test were employed to characterize the structure and performance of the catalyst. Results showed that the catalyst was amorphous carbon composed of aromatic carbon sheets with –COOH, –OH and –SO3H groups. Previous impregnation with H3PO4 could promote porosity formation of the catalyst. The optimized carbonization temperature and time for the catalyst were 250 °C and 1.5 h. The –SO3H density and specific surface area for the catalyst prepared under the optimized conditions were 1.1 mmol g−1 and 118 m2 g−1, respectively. Compared to HZSM-5, Amberlyst-15 and previous reported carbon catalysts, the catalyst showed higher catalytic activity for transesterification of methyl acetate with n-butanol as hydrophobic reaction. The catalyst had good thermal stability, which could bear 200 °C without decomposition. The catalyst retained satisfactory catalytic activity for transesterification of methyl acetate after 8 reaction cycles.
Nanodimensional pores of metal-exchanged zeolite Y containing 5,10,15,20-tetra(4-methoxyphenyl)porphyrin have been prepared by the template “ship-in-a-bottle” method. This approach requires four pyrrole molecules and four 4-methoxy benzaldehyde molecules to diffuse into the pores of FeIII, MnIII and CoIII-exchanged zeolite Y. The host–guest nanocomposite materials have been applied to catalyze the epoxidation of (R)-(+)-limonene, using H2O2/ammonium acetate, at a defined temperature and atmospheric pressure. The encapsulated iron(III) complex is catalytically very efficient as compared to manganese(III) and cobalt(III) complexes for the partial epoxidation of (R)-(+)-limonene and is stable to be recycled without much deterioration. All catalytic systems have been characterized by UV/Vis diffuse reflectance spectroscopic, X-ray diffraction, BET, scanning electron microscopy and energy dispersive X-ray spectrometry analyses to confirm the immobilization of complexes.
Authors:Chun-Ni Fan, Cheng-Hua Xu, Chuan-Qi Liu, Zun-Yu Huang, Jian-Ying Liu, and Zhi-Xiang Ye
TiO2–SiO2 catalysts for glycerol acetalization with acetone are synthesized by the sol–gel method and characterized by N2 adsorption–desorption, X-ray diffraction, NH3-temperature programmed desorption, Fourier transform infrared spectroscopy and ultraviolet–visible diffuse reflectance spectroscopy techniques in the present work. The effects of catalyst preparation and acetalization parameters such as reaction time, acetone/glycerol ratio, catalyst amount and reaction temperature on acetalization are investigated simultaneously. Pyridine adsorption results indicate that Ti–Si mixed oxides naturally only consist of Lewis acidic sites. The results of catalyst preparation and characterization show that Br⊘nsted acidic sites can be produced after Ti–Si mixed oxides adsorb water molecules, and TiO2–SiO2 (Si/Ti = 1) calcined at 550 °C exhibits the most total acidic density leading to the highest catalytic property in glycerol acetalization. The glycerol catalytic acetalization mainly occurs on the Br⊘nsted acidic sites. The effects of acetalization parameters indicate that the formation of the main product 5-membered ring ketal 2,2-dimethyl-1,3-dioxolane-4-yl methanol (about 90 %) is governed by kinetics. About 95 % glycerol conversion in acetalization is obtained under the optimum conditions.