Resolution of the mechanism of CO electrooxidation on steady state and evaluation of the kinetic parameters for Pt and Ru electrodes

The carbon monoxide oxidation reaction (COOR) was studied on steady-state conditions by chronoamperometry on polycrystalline smooth platinum and ruthenium rotating disc electrodes in CO-saturated acid solution. The chronoamperometric response did not show current oscillations and therefore the current density (j) vs. overpotential (η) curves on steady state could be obtained. In order to interpret these results, kinetic expressions were derived starting from the mechanism proposed by S. Gilman, which considers two adsorbed reaction intermediates, carbon monoxide (CO_ad) and hydroxyl (OH_ad). Analytical expressions as a function of overpotential for the current density, the surface coverage of the adsorbed species (θ _CO and θ _OH) and the CO and CO₂ pressures at the electrode surface on steady state were obtained. This set of equations was used for the correlation of the experimental polarization curves and the evaluation of the corresponding kinetic parameters. From these values, the dependences of the surface coverage of the adsorbed intermediates on overpotential were simulated, as well as those of the partial pressure of CO and CO₂. Thus, it was demonstrated that the Gilman’s mechanism accurately describes the experimental results on steady state of the COOR on these metals.     

Platinum-catalysed bisindolylation of allenes: a complementary alternative to gold catalysis

Pt versus Au: Platinum-catalysed addition of nucleophiles to allenes follows a distinctly different pathway to the process catalysed by gold(I) complexes; the platinum catalyst leads to different products with indoles involving a bisindolylation reaction, whereas gold(I) gives allyl indoles from a single addition (see scheme).     

Sensitive and fast determination of Sudan dyes in chili powder by partial-filling micellar electrokinetic chromatography-tandem mass spectrometry

A fast and sensitive method for the simultaneous determination of Sudan dyes (I, II, III, and IV) in food samples was developed for the first time using partial filling micellar electrokinectic chromatography-mass spectrometry (MEKC-MS). The use of MEKC was essential to achieve the separation of these neutral analytes, while the partial filling technique was necessary to avoid the contamination of the ion source with non-volatile micelles. MEKC separation and MS detection conditions were optimized in order to achieve a fast, efficient, and sensitive separation of the four dyes. Filling 25% of the capillary with an MEKC solution containing 40 mM ammonium bicarbonate, 25 mM SDS, and 32.5% (v/v) acetonitrile, a baseline separation of the four azo-dyes was obtained in 10 min. Tandem MS was investigated in order to improve the sensitivity and selectivity of the analysis. Limits of detection (LOD) values 5, 8, 15, and 29 times better were obtained for Sudan III, I, II, and IV, respectively, using partial filling MEKC-MS/MS instead of partial filling MEKC-MS. Under optimized conditions, LOD from 0.05 to 0.2 μg/mL were obtained. The suitability of the developed method was demonstrated through the fast and sensitive determination of Sudan I, II, III, and IV in spiked chilli powder samples. This determination could not be achieved by MEKC-UV due to the existence of several interfering compounds from the matrix.     

An amine-catalyzed enantioselective [3+2] cycloaddition of azomethine ylides and α,β-unsaturated aldehydes: applications and mechanistic implications

The catalytic enantioselective [3+2] cycloaddition between azomethine ylides and α,β-unsaturated aldehydes catalyzed by α,α-diphenylprolinol has been studied in detail. In particular, the reaction has been extended to the use of 2-alkenylidene aminomalonates generated in situ as azomethine ylide precursors. These reactions lead to the formation of pyrrolidines containing a 5-alkenyl side chain with potential for chemical manipulation. Moreover, a detailed and concise computational study has been carried out to understand the exact nature of the mechanism of this reaction and especially the consequences derived from the incorporation of the chiral secondary amine catalyst on the reaction pathway.     

Poly(2,5-dimercapto-1,3,4-thiadiazole) as a cathode for rechargeable lithium batteries with dramatically improved performance

Organosulfur compounds with multiple thiol groups are promising for high gravimetric energy density electrochemical energy storage. We have synthesized a poly(2,5-dimercapto-1,3,4-thiadiazole) (PDMcT)/poly(3,4-ethylenedioxythiophene) (PEDOT) composite cathode for lithium-ion batteries with a new method and investigated its electrochemical behavior by charge/discharge cycles and cyclic voltammetry (CV) in an ether-based electrolyte. Based on a comparison of the electrochemical performance with a carbonate-based electrolyte, we found a much higher discharge capacity, but also a very attractive cycling performance of PDMcT by using a tetra(ethylene glycol) dimethyl ether (TEGDME)-based electrolyte. The first discharge capacity of the as-synthesized PDMcT/PEDOT composite approached 210 mAh g(-1) in the TEGDME-based electrolyte. CV results clearly show that the redox reactions of PDMcT are highly reversible in this TEGDME-based electrolyte. The reversible capacity remained around 120 mAh g(-1) after 20 charge/discharge cycles. With improved cycling performance and very low cost, PDMcT could become a very promising cathode material when combined with a TEGDME-based electrolyte. The poor capacity in the carbonate-based electrolyte is a consequence of the irreversible reaction of the DMcT monomer and dimer with the solvent, emphasizing the importance of electrolyte chemistry when studying molecular-based battery materials.     

Determination of lipoic acid, Trolox methyl ether and tocopherols in human plasma by liquid-chromatography and ion-trap tandem mass spectrometry

A method for the simultaneous determination of lipoic acid and/or Trolox methyl ether, along with α‐, γ‐ and δ‐tocopherol was developed using liquid chromatography–tandem mass spectrometry with negative electrospray ionization (HPLC‐ESI‐MS/MS) in an ion‐trap mass spectrometer. Detection and quantification were accomplished by a multiple reaction monitoring method, using specific transitions from precursor ion to product ion for each analyte. Chromatographic separation was achieved in a 12 min run using a C₁₈‐bonded phase and methanol–aqueous ammonium acetate elution gradient. Linear correlations of the chromatographic peak area (r.u. × s^?1) to the injected amount (ng) gave the slope values (r.u. × s^?1 × ng^?1) 2.34 × 10⁴ for α‐tocopherol, 5.05 × 10⁴ for γ‐tocopherol, 1.27 × 10⁵ for δ‐tocopherol, 8.86 × 10⁵ for lipoic acid and 1.23 × 10⁵ for Trolox methyl ether. The lower limit of quantification ranged between 0.02 and 1.22 ng for Trolox methyl ether and lipoic acid. MS³ experiments of γ‐ and δ‐tocopherol suggest ion‐radical reactions and dependence of the tocopherol fragmentation pattern on the phenolic ring methylation degree. The method is shown to be applicable to measurement of these metabolites in human serum after extraction. Copyright © 2012 John Wiley & Sons, Ltd.     

The artemisia L. Genus: a review of bioactive essential oils

Numerous members of the Anthemideae tribe are important as cut flowers and ornamental crops, as well as being medicinal and aromatic plants, many of which produce essential oils used in folk and modern medicine and in the cosmetics and pharmaceutical industry. Essential oils generally have a broad spectrum of bioactivity, owing to the presence of several active ingredients that work through various modes of action. Due to their mode of extraction, mostly by distillation from aromatic plants, they contain a variety of volatile molecules such as terpenes, phenol-derived aromatic and aliphatic components. The large genus Artemisia L., from the tribe Anthemideae, comprises important medicinal plants which are currently the subject of phytochemical attention due to their biological and chemical diversity. Artemisia species, widespread throughout the world, are one of the most popular plants in Chinese traditional preparations and are frequently used for the treatment of diseases such as malaria, hepatitis, cancer, inflammation and infections by fungi, bacteria and viruses. Extensive studies of the chemical components of Artemisia have led to the identification of many compounds as well as essentials oils. This review summarizes some of the main reports on the chemistry and anti-infective activities of Artemisia. Li. essential oils from the data in the recent literature (2000-2011).     

Electrical conductivity and luminescence in coordination polymers based on copper(I)-halides and sulfur-pyrimidine ligands

The solvothermal reactions between pyrimidinedisulfide (pym(2)S(2)) and CuI or CuBr(2) in CH(2)Cl(2):CH(3)CN lead to the formation of [Cu(11)I(7)(pymS)(4)](n) (pymSH = pyrimidine-2(1H)-thione) (1) and the dimer [Cu(II)(μ-Br)(Br)L](2) (L = 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde) (2). In the later reaction, there is an in situ S-S, S-C(sp(2)), and C(sp(2))-N multiple bond cleavage of the pyrimidinedisulfide resulting in the formation of 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde. Interestingly, similar reactions carried out just with a change in the solvent (H(2)O:CH(3)CN instead of CH(2)Cl(2):CH(3)CN) give rise to the formation of coordination polymers with rather different architectures. Thus, the reaction between pym(2)S(2) and CuI leads to the formation of [Cu(3)I(pymS)(2)](n) (3) and [CuI(pym(2)S(3))] (pym(2)S(3) = pyrimidiltrisulfide) (4), while [Cu(3)Br(pymS)(2)](n) (5) is isolated in the reaction with CuBr(2). Finally, the solvothermal reactions between CuI and pyrimidine-2-thione (pymSH) in CH(2)Cl(2):CH(3)CN at different ratios, 1:1 or 2:1, give the polymers [Cu(2)I(2)(pymSH)(2)](n) (6) and [Cu(2)I(2)(pymSH)](n) (7), respectively. The structure of the new compounds has been determined by X-ray diffraction. The studies of the physical properties of the novel coordination polymers reveal that compounds 3 and 5 present excellent electrical conductivity values at room temperature, while compounds 1, 3, and 5-7 show luminescent strong red emission at room temperature.     

Contact line extraction and length measurements in model sediments and sedimentary rocks

The mechanisms that govern the transport of colloids in the unsaturated zone of soils are still poorly understood, because of the complexity of processes that occur at pore scale. These mechanisms are of specific interest in quantifying water quality with respect to pathogen transport (e.g. Escherichia coli, Cryptosporidium) between the source (e.g. farms) and human users. Besides straining in pore throats and constrictions of smaller or equivalent size, the colloids can be retained at the interfaces between air, water, and grains. Theories competing to explain this mechanism claim that retention can be caused by adhesion at the air-water-interface (AWI) between sediment grains or by straining at the air-water-solid (AWS) contact line. Currently, there are no established methods for the estimation of pathogen retention in unsaturated media because of the intricate influence of AWI and AWS on transport and retention. What is known is that the geometric configuration and connectivity of the aqueous phase is an important factor in unsaturated transport. In this work we develop a computational method based on level set functions to identify and quantify the AWS contact line (in general the non-wetting-wetting-solid contact line) in any porous material. This is the first comprehensive report on contact line measurement for fluid configurations from both level-set method based fluid displacement simulation and imaged experiments. The method is applicable to any type of porous system, as long as the detailed pore scale geometry is available. We calculated the contact line length in model sediments (packs of spheres) as well as in real porous media, whose geometry is taken from high-resolution images of glass bead packs and sedimentary rocks. We observed a strong dependence of contact line length on the geometry of the sediment grains and the arrangement of the air and water phases. These measurements can help determine the relative contribution of the AWS line to pathogen retention.     

Surfactant (bi)layers on gold nanorods

Gold nanorods in aqueous solution are generally surrounded by surfactants or capping agents. This is crucial for anisotropic growth during synthesis and for their final stability in solution. When CTAB is used, a bilayer has been evidenced from analytical methods even though no direct morphological characterization of the precise thickness and compactness has been reported. The type of surfactant layer is also relevant to understand the marked difference in further self-assembling properties of gold nanorods as experienced using 16-EO(1)-16 gemini surfactant instead of CTAB. To obtain a direct measure of the thickness of the surfactant layer on gold nanorods synthesized by the seeded growth method, we coupled TEM, SAXS, and SANS experiments for the two different cases, CTAB and gemini 16-EO(1)-16. Despite the strong residual signal from micelles in excess, it can be concluded that the thickness is imposed by the chain length of the surfactant and corresponds to a bilayer with partial interdigitation.