Kinetic and mechanistic investigation of the ozonolysis of 2,4-xylidine (2,4-dimethyl-aniline) in acidic aqueous solution

The ozonolysis of 2,4-xylidine (2,4-dimethyl-aniline) in acidic aqueous solution was investigated by determining the major reaction products and their evolution as a function of the reaction time and their dependence on the pH of the reaction system. 2,4-Dimethyl-nitrobenzene and 2,4-dimethyl-phenol were found to be primary reaction products; their formation might be explained by electron transfer and substitution reactions. 2,4-Dimethyl-phenol was further oxidized yielding 2,4-dimethyl- and/or 4,6-dimethyl-resorcinol by electrophilic addition of HO(center dot) radicals. The best fitting phenomenological kinetic model and the good convergence of calculated and experimentally determined rate constants imply two additional competitive pathways of substrate oxidation: (i) electrophilic addition of HO(center dot) radicals and fast subsequent substitution would also yield the resorcinol derivatives. (ii) Substrate and isolated products are thought to be oxidized by hydrogen abstraction at the benzylic sites, but the corresponding products (alcohols, aldehydes, and carboxylic acids) could not be identified. Fe(II) was added to probe for the presence of H(2)O(2), but had no or only a minor effect on the kinetics of the ozonolysis. (c) 2009 Elsevier B.V. All rights reserved.

Spectroscopic evidences of the presence of hydrogenated species on the surface of copper during CO(2) electroreduction at low cathodic potentials

Carbon dioxide electroreduction on copper electrode was studied by surface enhanced Raman scattering (SERS) in K(2)SO(4) aqueous solutions with different pH values. CO(2) was bubbled into the solution at 0 V vs. Ag/AgCl, i.e., on an oxidized copper surface. In acidic solutions (pH around 2.5), at -0.2 V, bands indicative of the presence of ethylene on the electrode surface were detected. Although ethylene is knowledgably a product of CO(2) electroreduction on copper, it was not experimentally identified on the electrode`s surface at such a low cathodic potential in prior works. In solutions with pH around 2.5, CO bands were not observed, suggesting that hydrocarbons could be formed by a pathway that does not occur via adsorbed CO. In solutions with higher pHs, a complex spectral pattern, between 800 and 1700 cm(-1), was observed at approximately -0.4 V. The observed spectrum closely resembles those reported in the literature for adsorption of monocarboxylic acids with small chains. The spectral features indicate the presence of a structure containing a double C=C bond. a carboxyl group, and C-H bonds on the electrode`s surface. SERS spectra obtained in CO-saturated solution are also presented. However, in this case, no SERS bands were observed in the region between 800 and 1700 cm(-1) at low cathodic potentials. (c) 2009 Elsevier B.V. All rights reserved.

Raman evidence of the interaction between multiwalled carbon nanotubes and nanostructured TiO(2)

Nanocomposites of carbon nanotubes and titanium dioxide (TiO(2)) have attracted much attention due to their photocatalytic properties. Although many examples in the literature have visualized these nanocomposites by electron microscopic images, spectroscopic characterization is still lacking with regard to the interaction between the carbon nanotube and TiO(2). In this work, we show evidence of the attachment of nanostructured TiO(2) to multiwalled carbon nanotubes(MWNTs) by Raman spectroscopy. The nanostructured TiO(2) was characterized by both full-width at half-maximum (FWHM) and the Raman shift of the TiO(2) band at ca 144 cm(-1), whereas the average diameter of the crystallite was estimated as approximately 7 nm. Comparison of the Raman spectra of the MWNTs and MWNTs/TiO(2) shows a clear inversion of the relative intensities of the G and D bands, suggesting a substantial chemical modification of the outermost tubes due to the attachment of nanostructured TiO(2). To complement the nanocomposite characterization, scanning electronic microscopy and X-ray diffraction were performed. Copyright (C) 2011 John Wiley & Sons, Ltd.

Preparation and characterization of the novels terpolymers of poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} and styrene-divinylbenzene-vinylpiridine impregnated with silver nanoparticles

This paper reports the preparation and characterization of poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} and styrene-divinylbenzene-vinylpiridine filled with nanosilver. Theses materials were synthesized by non aqueous polymerization through a chemical reaction using benzoyl peroxide as the initiator. The nanosilver was obtained from chemical reduction using NaBH(4) as reducing agent and sodium citrate as stabilizer. The nanometric dimension of nanosilver was monitored by UV-visible and confirmed through TEM. The morphology was characterized by SEM and the thermal properties were done by TGA and DSC. The antimicrobial action of the polymers impregnated with nanosilver was evaluated using both microorganisms, Staphylococcus aureus and Escherichia coli. The antimicrobial activity of the poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} filled with nanosilver was confirmed by the presence of an inhibition halo of the bacterial growth in seeded culture media, but was not confirmed to the styrene-divinylbenzene-vinylpiridine. The present work suggest that trans - [RuCl(2)(vpy)(4)] complex facilitate the release of silver ion from the media.

A theoretical study of the binding and electronic spectrum of the Mo-2 molecule

Multiconfigurational SCF and second-order perturbation theory have been employed to study seven low-lying singlet and triplet electronic states of the Mo-2 molecule. The bond order of the ground state has been analyzed based on the effective bond order (EBO), indicating that a fully developed sextuple bond is formed between the two Mo atoms. The experimentally observed excited states a(3)Sigma(+)(u) and A(1)Sigma(+)(u) have been determined and the so-called (3)Lambda excited state identified as the b(3)Sigma(+)(u) state, in agreement with experimental expectations. (C) 2007 Elsevier B.V. All rights reserved.

Crosslinking of Poly(N-vinyl-2-pyrrolidone) in the Coating of Cotton Yarn

Coating of cotton yarn is employed in the textile industry to increase the mechanical resistance of the yarns and resistance to vibration, friction, impact, and elongation, which are some of the forces to which the yarn is subjected during the weaving process. The main objective of this study is to investigate the usage of a synthetic hydrophilic polymer, poly(N-vinyl-2-pyrrolidone) (PVP), to coat 100% cotton textile yarn, aiming to give the yarn a temporary mechanical resistance. For the improvement of the mechanical resistance of the yarn, the following crosslinking processes of PVP were investigated: UV-C (ultraviolet) radiation, the Fenton and photo-Fenton reactions, and sensitized UV-C radiation. The influence of each crosslinking process was determined through tensile testing of the coated yarns. The results indicated that the best crosslinking process employed was UV-C radiation; increasing the mechanical resistance of the yarn up to 44% if compared with the pure cotton yarn, that is, without polymeric coating and crosslinking. POLYM. ENG. SCI., 51:445-453, 2011. (C) 2010 Society of Plastics Engineers

Asymmetric phase-transfer catalytic sulfanylation of some 2-methylsulfinyl cyclanones. Modeling of the stereochemical course of the aldol reaction of (SS,2S)-2-methylsulfinyl-2-methylsulfanylcyclohexanone

Increased diastereoisomeric excesses are obtained for the sulfanylation reactions of some 2-methylsulfinyl cyclanones under phase-transfer catalysis using the chiral catalyst QUIBEC instead of TEBA. The optically pure (SS,2S)-2-methylsulfinyl-2-methylsulfanylcyclohexanone thus prepared reacts with ethyl acetate lithium enolate affording, after hydrolysis, (R)-2-[(ethoxycarbonyl)methyl]-2-hydroxycyclohexanone in 60% ee. Density functional theory calculations (at the B3LYP/6-311++G(d,p) level) can successfully explain the origin of this result as the kinetically favored axial attack of the nucleophile to the carbonyl group of the most stable conformer of the cyclanone, in which the CH(3)SO and CH(3)S groups are at the equatorial and axial positions, respectively. (C) 2010 Elsevier Ltd. All rights reserved.

Self-reinforced composites obtained by the partial oxypropylation of cellulose fibers. 2. Effect of catalyst on the mechanical and dynamic mechanical properties

This work describes the partial oxypropylation of filter paper cellulose fibers, employing two different basic catalyst, viz., potassium hydroxide and 1,4-diazabicyclo [2.2.2] octane, to activate the hydroxyl groups of the polysaccharide and thus provide the anionic initiation sites for the ""grafting-from"" polymerization of propylene oxide. The success of this chemical modification was assessed by FTIR spectroscopy, X-ray diffraction, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis and contact angle measurements. The study of the role of the catalyst employed on the extent of the modification and on the mechanical properties of the ensuing composites, after hot pressing, showed that both the Bronsted and the Lewis base gave satisfactory results, without any marked difference.

Effect of the Y(2)O(3)-ZrO(2) support composition on nickel catalyst evaluated in dry reforming of methane

Nickel catalysts with a load of 5 wt.% Ni, supported on pure ZrO(2) and ZrO(2) stabilized with 4 mol%, 8 mol% and 12 mol% of Y(2)O(3), were prepared by the polymerization method. The samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction with hydrogen (TPR-H(2)), specific surface area (BET) and electronic paramagnetic resonance (EPR) and tested as catalysts for carbon dioxide reforming of methane. The XRD patterns showed the presence of the oxide precursor (NiO) and the tetragonal phase of a Y(2)O(3)-ZrO(2) solid solution. According to the TPR-H(2) analysis, the reduction of various NiO species was influenced by the composition of the support. Catalytic tests were conducted at 800 degrees C for 6 h, and the composition of the gaseous products and the catalytic conversion rate depended on the composition of the Y(2)O(3)-ZrO(2) solid solution and its influence on the supported NiO species. A direct relation was observed between the variation in the support, the nickel species supported on it and the performance in the catalytic tests. (C) 2008 Elsevier B.V. All rights reserved.

Co catalysts supported on SiO(2) and gamma-Al(2)O(3) applied to ethanol steam reforming: Effect of the solvent used in the catalyst preparation method

Cobalt catalysts were prepared on supports of SiO(2) and gamma-Al(2)O(3) by the impregnation method, using a solution of Co precursor in methanol. The samples were characterized by XRD, TPR, and Raman spectroscopy and tested in ethanol steam reforming. According to the XRD results, impregnation with the methanolic solution led to smaller metal crystallites than with aqueous solution, on the SiO(2) support. On gamma-Al(2)O(3), all the samples exhibited small crystallites, with either solvent, due to a higher Co-support interaction that inhibits the reduction of Co species. The TPR results were consistent with XRD results and the samples supported on gamma-Al(2)O(3) showed a lower degree of reduction. In the steam reforming of ethanol, catalysts supported on SiO(2) and prepared with the methanolic solution showed the best H(2), CO(2) and CO selectivity. Those supported on gamma-Al(2)O(3) showed lower H(2) selectivity. (C) 2011 Elsevier Ltd. All rights reserved.

Effects of the partial replacement of La by M (M=Ce, Ca and Sr) in La(2-x)M(x)CuO(4) perovskites on catalysis of the water-gas shift reaction

The performance of La(2-x)M(x)CuO(4) perovskites (where M = Ce, Ca or Sr) as catalysts for the water-gas shift reaction was investigated at 290 degrees C and 360 degrees C. The catalysts were characterized by EDS, XRD, N(2) adsorption-desorption, XPS and XANES. The XRD results showed that all the perovskites exhibited a single phase (the presence of perovskite structure), suggesting the incorporation of metals in the perovskite structure. The XPS and XANES results showed the presence of Cu(2+) on the surface. The perovskites that exhibited the best catalytic performance were La(2-x)Ce(x)CuO(4) perovslcites, with CO conversions of 85%-90%. Moreover, these perovskites have higher surface areas and larger amounts of Cu on the surface. And Ce has a higher filled energy level than the other metals, increasing the energy of the valence band of Ce and providing more electrons for the reaction. Besides, the La(1.80)Ca(0.20)CuO(4) perovskite showed a good catalytic performance.

Synthesis, characterization and biological analysis of the complex [VO(Hdhp)(2)] (H(2)dhp=2,3-dihydroxypyridine)

A new vanadium (IV) complex with the monoanion of 2,3-dihydroxypyridine (H(2)dhp), or 3-hydroxy-2(1H)-pyridone, was synthesized, characterized by physicochemical techniques and tested biologically. The EPR data for the [VO(Hdhp)(2)] complex in DMF are: g(x) = 1.9768, g(y) = 1.9768 and g(z) = 1.9390; A values (10(-4) cm(-1)): A(x), 59.4; A(y//), 59.4; A(z), 171.0. The vV=O band in the IR spectrum of the complex is at 986 cm(-1). The complex is paramagnetic, with mu(eff) = 1.65 BM (d(1), spin-only) at 25 degrees C. The irreversible oxidation process [V(V)/V(IV)] of the [VO(Hdhp)(2)] complex, as revealed in a cyclic voltammogram, occurs at 876 mV. The calculated molecular structure of [VO(Hdhp)(2)] shows the vanadium(IV) center in a distorted square pyramidal environment, with the oxo ligand in the apical position and the oxygen donor atoms of the Hdhp ligands in the basal positions. The ability of [VO(Hdhp)(2)] to mimic insulin, and its toxicity to hepato-biliary functions, were investigated in streptozotocin-induced diabetic rats and it was concluded that the length of treatment and the amount of [VO(Hdhp)(2)] administered were effective in reducing experimental diabetes.

An insight into the beginning stage of the aqueous ring opening metathesis polymerization of exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid with Ru(III) compounds: the consumption of Ru(III) species in the presence of carboxylic acids monitored by ESR spectroscopy

The presence of paramagnetic species in the aqueous ring opening metathesis polymerizations of the exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid monomer with RuCl(3) and K(2)[RuCl(5)H(2)O] compounds was studied using ESR techniques. It was observed that the intensities of the Ru(III) signals in the ESR spectra decrease on the time scale of the induction period so that the ROMP can take place. The intensity of the Ru(III) signal almost disappeared 50 min after reacting with K(2)[RuCl(5)H(2)O] and after 100 mm in the case of RuCl(3). Reactions of the cis-[Ru(NH(3))(4)(H(2)O)(2)](tfms)(3) and [Ru(NH(3))(5)H(2)O](tfms)(3) complexes with the monomer and different organic compounds representing the organic functions in the monomer (furan, norbornene, but-2-ene-1,4-diol and formic, acetic, oxalic and maleic acids) were also monitored by ESR and UV/vis spectra. It was deduced that the organic acids provide the disappearance of the Ru(III) signal. The proton NMR relaxation times of the residual water in D(2)O for reactions with oxalic acid suggested that the presence of paramagnetic ions in the solution decreases along with

Evaluation of Postpolymerization as a Function of the Storage Time of Triethylene Glycol Dimethacrylate/2,2-Bis[4-(2-Hydroxy-3-Methacryloxy-Prop-1-Oxy)-Phenyl]-propane Bisphenyl-alpha-Glycidyl Ether Dimethacrylate Copolymers Used in Dental Resins by Differential Scanning Calorimetry and Dynamic Mechanical Analysis

The aim of this work was to evaluate the effect of the storage time on the thermal properties of triethylene glycol dimethacrylate/2,2-bis[4-(2-hydroxy-3-methacryloxy-prop-1-oxy)-phenyl]propane bisphenyl-alpha-glycidyl ether dimethacrylate (TB) copolymers used in formulations of dental resins after photopolymerization. The TB copolymers were prepared by photopolymerization with an Ultrablue IS light-emitting diode, stored in the dark for 160 days at 37 degrees C, and characterized with differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and Fourier transform infrared spectroscopy with attenuated total reflection. DSC curves indicated the presence of an exothermic peak, confirming that the reaction was not completed during the photopolymerization process. This exothermic peak became smaller as a function of the storage time and was shifted at higher temperatures. In DMA studies, a plot of the loss tangent versus the temperature initially showed the presence of two well-defined peaks. The presence of both peaks confirmed the presence of residual monomers that were not converted during the photopolymerization process. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 679-684, 2009