The Mercury (II) Catalyzed,One-Pot Oxidation of Terminal Alkynes by Sodium Perborate in Acetic Acid

A series of terminal alkynes has been reacted with sodium perborate and mercuric acetate catalyst in acetic acid to produce 1-acetoxyalkan-2-ones in good yield. The reaction constitutes a mild and convenient method for the oxidation of terminal triple bonds.     

Combined protocol for the analysis of polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyls (PCBx) from sediments using focussed microwave assisted (FMW) extraction at atmospheric pressure

A microwave-assisted protocol has been developed using focussed microwaves at atmospheric pressure for the extraction of PAHs and PCBs from sediments. It combines extraction and purification assisted by microwaves. This protocol has been applied to the quantification of 12 individual PAHs, 8 individual PCBs and 8 PCB coeluted mixtures from two Standard Reference Materials and one natural sediment. The results for both classes of compounds (PAHs and PCBs) are good in terms of recoveries, which are always greater than 70% and in most cases around 100%. The reproducibility is also good with coefficients of variation below 10% in most cases. This protocol has the great advantage of saving time, the time dedicated to the preparation / extraction assisted by microwaves being reduced to less than half an hour.     

Surface chemical modification to control molecular interactions with porous silicon

Interactions between porous silicon (pSi) particles and probe molecules were evaluated to determine the effect of pSi and probe molecule chemistry on adsorption. Methylene blue, ethyl violet and orange G dyes were chosen for investigation as they possess distinct functionalities and charges. Several distinct pSi surface species were produced via thermal oxidation at 200-800 °C and their effect on adsorption investigated. The adsorption mechanisms were elucidated from equilibrium adsorption and desorption isotherms. Methylene blue adsorption was attributed to electrostatic attraction where a gradual increase in adsorption with oxidation temperature was observed. Significant methylene blue desorption was observed at pH 3, confirming adsorption occurs via electrostatic attraction. Ethyl violet demonstrated an increase in plateau adsorption capacity and affinity with increased oxidation temperatures and adsorption was initially attributed to electrostatic attraction, however desorption of ethyl violet was not observed, thus indicating potential chemisorption. Orange G exhibited high affinity adsorption for Si(y)SiH(x) terminated surfaces but no orange G desorption was detected, indicating a chemisorption adsorption mechanism. It has been successfully demonstrated that the surface modification of pSi enabled the manipulation of molecular interactions. By interacting probe molecules with similar functionalities to drug molecule with pSi, greater understanding of drug-pSi interactions can be ascertained which are of great importance. pSi surface chemistry can be tailored to enable control over molecular interactions and ultimately dictate loading, encapsulation and release behavior.     

Multi-matrix models from jet coefficients

We present a very natural framework in which to discuss multi-matrix models of two-dimensional quantum gravity. Multi-matrix model actions, string equations, and other quantities can be compactly expressed in terms of the jets of the resolvents of the relevant differential operators. This allows one to write down equations describing minimal matter coupled to two-dimensional quantum gravity directly in terms of known functionals.     

Mesoscopic resonating valence bond system on a triple dot

We theoretically introduce a mesoscopic pendulum from a triple dot. The pendulum is fastened through a singly occupied dot (spin qubit). Two other strongly capacitively coupled islands form a double-dot charge qubit with one electron in excess oscillating between the two low-energy charge states (1,0) and (0,1). The triple dot is placed between two superconducting leads. Under realistic conditions, the main proximity effect stems from the injection of resonating singlet (valence) bonds on the triple dot. This gives rise to a Josephson current that is charge- and spin-dependent and, as a consequence, exhibits a distinct resonance as a function of the superconducting phase difference.     

Elucidation of nitrate reduction pathways in anaerobic bioreactors using a stable isotope approach

Leachate recirculation allows an increase of moisture content and the enhancement of the anaerobic digestion of wastes in landfill. Since there is no ammonia elimination process in landfill when leachate is recirculated, NH(4) (+) may accumulate. One strategy for NH(4) (+) removal is to treat aerobically the leachate outside the landfill to convert NH(4) (+) into NO(3) (-). When nitrified leachate is recirculated, denitrification should occur in the waste. We have previously shown that wastes have a large capacity to convert nitrate into N(2). Nevertheless, in some cases we observed nitrate reduction without gaseous nitrogen production. Using a stepwise multiple regression models, H(2)S concentration was the unique parameter found to have a negative effect on N(2) production. We then suspected that dissimilatory nitrate reduction to ammonium (DNRA) occurred in the presence of H(2)S. In order to verify this hypothesis, (15)N nitrate injections were performed into microcosms containing different H(2)S concentrations. The ammonium (15)N enrichment was measured using an elemental analyser coupled to an isotope ratio mass spectrometer. In the two microcosms containing the highest H(2)S concentrations, the ammonium was (15)N enriched and at the end of the experiment all the added nitrate was converted into ammonium. For the two microcosms containing the lowest H(2)S concentrations, no (15)N enrichment of ammonium was observed. This isotopic approach has allowed us to demonstrate that, in the presence of significant concentrations of H(2)S, denitrification is replaced by DNRA.     

Multi-residue analysis of polycyclic aromatic hydrocarbons, polychlorobiphenyls, and organochlorine pesticides in marine sediments

A multi-residue analysis procedure using microwave-assisted extraction and pre-purification has been developed for the combined analysis of polycyclic aromatic hydrocarbons (PAH), polychlorobiphenyls (PCB), and organochlorine pesticides (OCP) in marine sediments. This procedure has been validated with certified marine sediment. Several surrogate standards have been employed and the use of octachloronaphthalene (OCN) as a surrogate standard for organochlorine determination in this matrix is discussed. The recoveries of all compounds were high (>70%) and the relative standard deviations are of the same order as the certified values. Different analytical problems are discussed, including DDT degradation in gas chromatography and laboratory PCB background levels. Quantification problems encountered for two pesticides (cis-chlordane and trans-nonachlor) were attributed to PAH interference in the GC-ECD chromatogram.     

Hidden Caldeira-Leggett dissipation in a Bose-Fermi Kondo model

We show that the Bose-Fermi Kondo model (BFKM), which may find applicability both to certain dissipative mesoscopic qubit devices and to heavy-fermion systems described by the Kondo lattice model, can be mapped exactly onto the Caldeira-Leggett model. This mapping requires an ohmic bosonic bath and an Ising-type coupling between the latter and the impurity spin. This allows us to conclude unambiguously that there is an emergent Kosterlitz-Thouless quantum phase transition in the BFKM with an ohmic bosonic bath. By applying a bosonic numerical renormalization group approach, we thoroughly probe physical quantities close to the quantum phase transition.