The role of the steps in the cleavage of the C-C bond during ethanol oxidation on platinum electrodes

Ethanol oxidation has been studied on stepped platinum single crystal electrodes in acid media using electrochemical and Fourier transform infrared (FTIR) techniques. The electrodes used belong to two different series of stepped surfaces: those having (111) terraces with (100) monoatomic steps and those with (111) terraces with (110) monoatomic steps. The behaviors of the two series of stepped surfaces for the oxidation of ethanol are very different. On the one hand, the presence of (100) steps on the (111) terraces provides no significant enhancement of the activity of the surfaces. On the other hand, (110) steps have a double effect on the ethanol oxidation reaction. At potentials below 0.7 V, the step catalyzes the C-C bond cleavage and also the oxidation of the adsorbed CO species formed. At higher potentials, the step is not only able to break the C-C bond, but also to catalyze the oxidation of ethanol to acetic acid and acetaldehyde. The highest catalytic activity from voltammetry for ethanol oxidation was obtained with the Pt(554) electrode.

Spectroscopic and electrochemical properties of iron(II) complexes of polydentate Schiff bases containing pyrazine, pyridine and imidazole groups

We report the synthesis and spectroscopic/electrochemical properties of iron(II) complexes of polydentate Schiff bases generated from 2-acetylpyridine and 1,3-diaminopropane, acetylpyrazine and 1,3-diaminopropane, and from 2-acetylpyridine and L-histidine. The complexes exhibit bis(diimine)iron(II) chromophores in association with pyrazine, pyridine or imidazole groups displaying contrasting pi-acceptor properties. In spite of their open geometry, their properties are much closer to those of macrocyclic tetraimineiron(II) complexes. An electrochemical/spectroscopic correlation between E degrees(Fe(III/II)) and the energies of the lowest MLCT band has been observed, reflecting the stabilization of the HOMO levels as a consequence of the increasing backbonding effects in the series of compounds. Mossbauer data have also confirmed the similarities in their electronic structure, as deduced from the spectroscopic and theoretical data. (C) 2008 Elsevier B.V. All rights reserved.

Effect of W on PtSn/C catalysts for ethanol electrooxidation

Binary and ternary Pt-based catalysts were prepared by the Pechini-Adams modified method on carbon Vulcan XC-72, and different nominal compositions were characterized by TEM and XRD. XRD showed that the electrocatalysts consisted of the Pt displaced phase, suggesting the formation of a solid solution between the metals Pt/W and Pt/Sn. Electrochemical investigations on these different electrode materials were carried out as a function of the electrocatalyst composition, in acid medium (0.5 mol dm(-3) H2SO4) and in the presence of ethanol. The results obtained at room temperature showed that the PtSnW/C catalyst display better catalytic activity for ethanol oxidation compared to PtW/C catalyst. The reaction products (acetaldehyde, acetic acid and carbon dioxide) were analyzed by HPLC and identified by in situ infrared reflectance spectroscopy. The latter technique also allowed identification of the intermediate and adsorbed species. The presence of linearly adsorbed CO and CO2 indicated that the cleavage of the C-C bond in the ethanol substrate occurred during the oxidation process. At 90 degrees C, the Pt85Sn8W7/C catalyst gave higher current and power performances as anode material in a direct ethanol fuel cell (DEFC).

3-Nitrophenol-4,4 '-bipyridyl N,N '-dioxide (2/1): a DFT study and CSD analysis of DPNO molecular complexes

The title 2:1 complex of 3-nitrophenol (MNP) and 4,4'-bipyridyl N, N'-dioxide (DPNO), 2C(6)H(5)NO(3)center dot C(10)H(8)N(2)O(2) or 2MNP center dot DPNO, crystallizes as a centrosymmetric three-component adduct with a dihedral angle of 59.40 (8)degrees between the planes of the benzene rings of MNP and DPNO (the DPNO moiety lies across a crystallographic inversion centre located at the mid-point of the C-C bond linking its aromatic rings). The complex owes its formation to O-H center dot center dot center dot O hydrogen bonds [O center dot center dot center dot O = 2.605 (3) angstrom]. Molecules are linked by intermolecular C-H center dot center dot center dot O and C-H center dot center dot center dot N interactions forming R(2)(1) (6) and R(2)(2) (10) rings, and R(6)(6) (34) and R(4)(4) (26) macro-rings, all of which are aligned along the [(1) over bar 01] direction, and R(2)(2) (10) and R(2)(1) (7) rings aligned along the [010] direction. The combination of chains of rings along the [(1) over bar 01] and [010] directions generates the three-dimensional structure. A total of 27 systems containing the DNPO molecule and forming molecular complexes of an organic nature were analysed and compared with the structural characteristics of the dioxide reported here. The N-O distance [1.325 (2) angstrom] depends not only on the interactions involving the O atom at the N-O group, but also on the structural ordering and additional three-dimensional interactions in the crystal structure. A density functional theory (DFT) optimized structure at the B3LYP/6-311G(d,p) level is compared with the molecular structure in the solid state.

Catalytic oxidation of ethanol on gold electrode in alkaline media

This work presents a study of the catalytic oxidation of ethanol on polycrystalline gold electrode in alkaline media. The investigation was carried out by means of chronoamperometry, cyclic voltammetry, and in situ FTIR spectroscopy. The main goal was to investigate the early stages of ethanol electrooxidation, namely at fairly low potentials (E = 600 mV vs. RHE) and for moderate reaction times (t < 300 s). Chronoamperometric experiments show a current increase accompanying the increasing in the ethanol concentration up to about 2 M and then a slight decrease at 3 M. Adsorbed CO has been observed as early as about 200 mV vs. RHE and indicates that the cleavage of the C-C bond might occur, probably to a small extent, at very low overpotentials during ethanol adsorption on gold surface. The amount of dissolved acetate ions produced during the chronoamperomentry was followed by the asymmetric stretching band at 1558 cm(-1) as a function of time, and found to increase linearly with time up to 300 s. This allowed estimating the reaction order of acetate formation with respect to ethanol concentration.

Surface structure effects on the electrochemical oxidation of ethanol on platinum single crystal electrodes

Ethanol oxidation has been studied on Pt(111), Pt(100) and Pt(110) electrodes in order to investigate the effect of the surface structure and adsorbing anions using electrochemical and FTIR techniques. The results indicate that the surface structure and anion adsorption affect significantly the reactivity of the electrode. Thus, the main product of the oxidation of ethanol on the Pt(111) electrode is acetic acid, and acetaldehyde is formed as secondary product. Moreover, the amount of CO formed is very small, and probably associated with the defects present on the electrode surface. For that reason, the amount of CO(2) is also small. This electrode has the highest catalytic activity for the formation of acetic acid in perchloric acid. However, the formation of acetic acid is inhibited by the presence of specifically adsorbed anions, such as (bi) sulfate or acetate, which is the result of the formation of acetic acid. On the other hand, CO is readily formed at low potentials on the Pt(100) electrode, blocking completely the surface. Between 0.65 and 0.80 V, the CO layer is oxidized and the production of acetaldehyde and acetic acid is detected. The Pt(110) electrode displays the highest catalytic activity for the splitting of the C-C bond. Reactions giving rise to CO formation, from either ethanol or acetaldehyde, occur at high rate at any potential. On the other hand, the oxidation of acetaldehyde to acetic acid has probably the lower reaction rate of the three basal planes.

Ultrasound-assisted synthesis of symmetrical biaryls by palladium-catalyzed detelluration of 1,2-diaryiditellanes

An ultrasound-assisted synthesis of functionalized symmetrical biaryls with electron-withdrawing or electron-donating substituents is described and illustrated by the palladium-catalyzed detelluration of 1,2-diarylditellanes. This procedure offers easy access to symmetrical biaryls in short reaction time and the products are achieved in good to excellent yields. (c) 2009 Published by Elsevier Ltd.

New Mixed Li/Mg and Li/Mg/Zn Amides for the Chemoselective Metallation of Arenes and Heteroarenes

New mixed Li/Mg and Li/Mg/Zn amides have been synthesized starting from readily prepared secondary amines. They allow a highly chemoselective directed magnesiation or zincation of various polyfunctional aromatics and heteroaromatics. The kinetic basicity, solubility and stability of these new bases have been compared with those of the corresponding 2,2,6,6-tetramethylpiperamide-derived bases. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Synthesis of naturally occurring diene and trienes by Te/Li exchange on (1Z,3Z)-butyltelluro-4-methoxy-1,3-butadiene

(1Z,3Z)-Butyltelluro-o-4-methoxy-1,3-butadiene 2 was obtained by the hydrotelluration of(Z)-1-methoxy-but-1-en-3-ynes 1. The butadienyllithium 3 obtained by the Te/Li exchange reaction in the (1Z,3Z)-1-butyltelluro-4-methoxy-1.3-butadiene 2 reacted with aldehydes to form the corresponding alcohols 4a-d with total retention of configuration. The alcohols formed undergo hydrolysis, resulting in the alpha,beta,gamma,delta-unsaturated aldehydes of (E,E) configuration, which are precursors of trienes obtained from natural sources. The products of this reaction were employed in the synthesis of methyl-(2E,4E)-decadienoate 7, which is a component of the flavor principles of ripe Bartlett pears. Performing the Wittig reaction of the methyl triphenylphosphorane with the deca-(2E,4E)-dienal 5a, we were able to synthesize the undeca-(1,3E,5E)-triene 6a. This compound is a sex-pheromone component of the marine brown algae Fucus serratus, Dictyopteris plagiograma, and Dictyopteris australis. Performing the Wittig reaction of methyl triphenylphosphorane with the octa-(2E,4E)-dienal 5c, the nona-(1,3E,5E)-triene 6b was synthesized. The compound obtained is a sex-pheromone component of the marine brown alga Sargassum horneri. The octa-( 1,3E,5E)-triene 6c was easily obtained from hepta-(2E,4E)-dienal 5d by the Wittig reaction with methyl triphenylphophorane. This compound is a sex-pheromone component of the marine brown alga Fucus serratus. (C) 2010 Elsevier Ltd. All rights reserved.

Total synthesis of (+/-)-dihydroactinidiolide using selenium-stabilized carbenium ion

A new, short total synthesis of dihydroactinidiolide 1 is described using selenium carbenium ion-promoted carbon-carbon bond formation as the key step. Our synthetic strategy starts with a lactonization reaction between 1,3,3-trimethylcyclohexene 13 and alpha-chloro-alpha-phenylseleno ethyl acetate 14, affording the key intermediate, alpha-phenylseleno-gamma-butyro lactone 15, which reacted via a selenoxide elimination to the target compound 1. (C) 2009 Elsevier Ltd. All rights reserved.

Oligomerization of the cysteinyl-rich oligopeptidase EP24.15 is triggered by S-glutathionylation

Thimet oligopeptidase (EC 3.4.24.15; EP24.15) is a thiol-rich metallopeptidase ubiquitously distributed in mammalian tissues and involved in oligopeptide metabolism both within and outside cells. Fifteen Cys residues are present in the rat EP24.15 protein, seven are solvent accessible, and two are found inside the catalytic site cleft; no intraprotein disulfide is described. In the present investigation, we show that mammalian immunoprecipitated EP24.15 is S-glutathionylated. In vitro EP24.15 S-glutathionylation was demonstrated by the incubation of bacterial recombinant EP24.15 with oxidized glutathione concentration as low as 10 mu M. The in vitro S-glutathionylation of EP24.15 was responsible for its oxidative oligomerization to dimer and trimer complexes. EP24.15 immunoprecipitated from cells submitted to oxidative challenge showed increased trimeric forms and decreased S-glutathionylation compared to immunoprecipitated protein from control cells. Our present data also show that EP24.15 maximal enzymatic activity is maintained by partial S-glutathionylation, a mechanism that apparently regulates the protein oligomerization. Present results raise the possibility of an unconventional property of protein S-glutathionylation, inducing oligomerization by interprotein thiol-disulfide exchange. (c) 2007 Elsevier Inc. All rights reserved.

Infrared analysis of ion beam irradiated polymers

Irradiation with heavy ions can produce several modifications in the chain structure of polymers. These modifications can be related to scissioning and cross-linking of chemical bonds. which depend on the ion fluence and the density of energy deposited in the material. Stacked thin film Makrofol-KG (R) samples were irradiated with 350 MeV Au(26+) ions and FTIR absorption spectroscopy was used to determine the bond changes in the samples. Data on the absorption bands as a function of the fluence indicated a higher probability for simple-bonds scissioning than for double-bonds scissioning and no dependence on the number of double bonds breaking with ion fluence. Since sample irradiation was done in a non-track-overlapping regime, a novel process for double bonds formation is suggested: the excitation of a site in the material by only one incident ion followed by a double bond formation during the de-excitation process. (C) 2009 Elsevier B.V. All rights reserved.

Triple Structural Transition below Room Temperature in the Antifilarial Drug Diethylcarbamazine Citrate

A very unusual triple structural transition pattern below room temperature was observed for the antifilarial drug diethylcarbamazine citrate. Besides the first thermal, crystallographic, and vibrational investigations of this first-line drug used in clinical treatment for lymphatic filariasis, a noteworthy behavior with three structural transformations as a function of temperature was demonstrated by differential scanning calorimetry, Raman spectroscopy, and single-crystal X-ray diffractometry. Our X-ray data on single crystals allow for a complete featuring and understanding of all transitions, since the four structures associated with the three solid-solid phase transformations were accurately determined. Two of three structural transitions show an order-disorder mechanism and temperature hysteresis with exothermic peaks at 224 K (T(1)`) and 213 K (T(2)`) upon cooling and endothermic ones at 248 K (T(1)) and 226 K (T(2)) upon heating. The other transition occurs at 108 K (T(3)) and it is temperature-rate sensitive. Molecular displacements onto the (010) plane and conformational changes of the diethylcarbamazine backbone as a consequence of the C-H center dot center dot center dot N hydrogen bonding formation/cleavage between drug molecules explain the mechanism of the transitions at T(1)`/T(2). However, such changes are observed only on alternate columns of the drug intercalated by citrate chains, which leads to a doubling of the lattice period along the a axis of the 235 K structure with respect to the 150 and 293 K structures. At T(2)`/T(1), these structural alterations occur in all columns of the drug. At T(3), there is a rotation on the axis of the N-C bond between the carbamoyl moiety and an ethyl group of one crystallographically independent diethylcarbamazine molecule besides molecular shifts and other conformational alterations. The impact of this study is based on the fascinating finding in which the versatile capability of structural adaptation dependent on the thermal history was observed for a relatively simple organic salt, diethylcarbamazine citrate.

Single-wall carbon nanotubes modified with organic dyes: Synthesis, characterization and potential cytotoxic effects

This work deals with the covalent functionalization of single-wall carbon nanotubes (SWNTs) with phenosafranine (PS) and Nile Blue (NB) dyes. These dyes can act as photosensitizers in energy and electron transfer reactions, with a potential to be applied in photodynamic therapy. Several changes in the characteristic Raman vibrational features of the dyes suggest that a covalent modification of the nanotubes with the organic dyes occurs. Specifically, the vibrational modes assigned to the NH(2) moieties of the dyes are seen to disappear in the SWNT-dye nanocomposites, corroborating the bond formation between amine groups in the dyes and carboxyl groups in the oxidized nanotubes. The X-ray absorption (XANES) data also show, that the intense band at 398.6 eV attributed to 1s -> 2p pi* transition of the nitrogen of the aromatic PS ring, is shifted due to the bonding with the carbonic structure of the SWNTs. The cytotoxicity data of dyes-modified SWNT composites in the presence and absence of light shows that the SWNT-NB (4 mu g/mL) composite presents a good photodynamic effect, namely a low toxicity in the dark, higher toxicity in the presence of light and also a reduced dye photobleaching by auto-oxidation. (C) 2010 Elsevier B.V. All rights reserved.

Modelling water adsorption on Au(210) surfaces: II. Monte Carlo simulations

Canonical Monte Carlo simulations for the Au(210)/H(2)O interface, using a force field recently proposed by us, are reported. The results exhibit the main features normally observed in simulations of water molecules in contact with different noble metal surfaces. The calculations also assess the influence of the surface topography on the structural aspects of the adsorbed water and on the distribution of the water molecules in the direction normal to the metal surface plane. The adsorption process is preferential at sites in the first layer of the metal. The analysis of the density profiles and dipole moment distributions points to two predominant orientations. Most of the molecules are adsorbed with the molecular plane parallel to surface, while others adsorb with one of the O-H bonds parallel to the surface and the other bond pointing towards the bulk liquid phase. There is also evidence of hydrogen bond formation between the first and second solvent layers at the interface. (c) 2007 Elsevier B.V. All rights reserved.