Electrical probe diagnostics for the laminar flame quenching distance

A simplified theory, previously developed for the general case of weakly ionized gas flow, is used to predict electrical probe response when the flame is quenched on the probe surface. This theory is based on the planar model of space charge sheaths around the measuring electrode. For the flame quenching case, by assuming that the sheath thickness is comparable with the thermal boundary layer thickness, probe current can be related to flame quenching distance. The theoretical assumptions made to obtain the analytical formulation of probe current were experimentally proved by using direct visualization and high-frequency PIV. The direct visualization method was also used to validate the results of flame quenching distance values obtained with electrical probe. The electrical probe diagnostics have been verified for both head-on and sidewall flame quenching regimes and for stoichiometric methane/air and propane/air mixtures in a pressure range of 0.05–0.6 MPa.     

Boron-capped tris(glyoximato) cobalt clathrochelate as a precursor for the electrodeposition of nanoparticles catalyzing H2 evolution in water

Electrochemical investigation of a boron-capped tris(glyoximato)cobalt clathrochelate complex in the presence of acid reveals that the catalytic activity toward hydrogen evolution results from an electrodeposition of cobalt-containing nanoparticles on the electrode surface at a modest cathodic potential. The deposited particles act as remarkably active catalysts for H(2) production in water at pH 7.     

New dicarboxylic acid bipyridine ligand for ruthenium polypyridyl sensitization of TiO2

An ambidentate dicarboxylic acid bipyridine ligand, (4,5-diazafluoren-9-ylidene) malonic acid (dfm), was synthesized for coordination to Ru(II) and mesoporous nanocrystalline (anatase) TiO(2) thin films. The dfm ligand provides a conjugated pathway from the pyridyl rings to the carbonyl carbons of the carboxylic acid groups. X-ray crystal structures of [Ru(bpy)(2)(dfm)]Cl(2) and the corresponding diethyl ester compound, [Ru(bpy)(2)(defm)](PF(6))(2), were obtained. The compounds displayed intense metal-to-ligand charge transfer (MLCT) absorption bands in the visible region (ε > 11,000 M(-1) cm(-1) for [Ru(bpy)(2)(dfm)](PF(6))(2) in acetonitrile). Significant room temperature photoluminescence, PL, was absent in CH(3)CN but was observed at 77 K in a 4:1 EtOH:MeOH (v:v) glass. Cyclic voltammetry measurements revealed quasi-reversible Ru(III/II) electrochemistry. Ligand reductions were quasi-reversible for the diethyl ester compound [Ru(bpy)(2)(defm)](2+), but were irreversible for [Ru(bpy)(2)(dfm)](2+). Both compounds were anchored to TiO(2) thin films by overnight reactions in CH(3)CN to yield saturation surface coverages of 3 × 10(-8) mol/cm(2). Attenuated total reflection infrared measurements revealed that the [Ru(bpy)(2)(dfm)](2+) compound was present in the deprotonated carboxylate form when anchored to the TiO(2) surface. The MLCT excited states of both compounds injected electrons into TiO(2) with quantum yields of 0.70 in 0.1 M LiClO(4) CH(3)CN. Micro- to milli-second charge recombination yielded ground state products. In regenerative solar cells with 0.5 M LiI/0.05 M I(2) in CH(3)CN, the Ru(bpy)(2)(dfm)/TiO(2) displayed incident photon-to-current efficiencies of 0.7 at the absorption maximum. Under the same conditions, the diethylester compound was found to rapidly desorb from the TiO(2) surface.     

Unexpected palladium catalyzed O-arylation occurring in 4-(4-fluoro-3-nitrophenyl)-1,2-dimethyl-5-nitro-1H-imidazole series

We describe herein a new unexpected palladium-catalyzed O-arylation reaction in fluorinated nitro(o-nitrophenyl)imidazole series involving arylboronic acids under Suzuki-Miyaura cross-coupling reaction conditions.     

A digital Compton suppression spectroscopy without gamma-ray coincidence-summing loss using list-mode multispectral data acquisition

The study demonstrates the advantages of an innovative list-mode multispectral data acquisition system that allows simultaneous creation of several different single, summed, coincident and anticoincident spectra with a single measurement. One of the consequences of list-mode data file offline processing is a reconstructed spectrum with Compton continuum suppression and without any full-energy peak efficiency deduction owing to true coincidence summing. The spectrometer is designed to read out analogue signal from preamplifier of gamma-ray detectors and to digitalize it using DGF/Pixie-4 software and card package (XIA LLC). This is realized by converting an Ortec Compton suppression data acquisition system into an all-digital spectrometer. Instead of using its timing electronic chain to determine the coincidence event, the analog signals from primary and guard detectors were connected directly into the Pixie-4 card for pulse height and time coincident measurement by individually logging and time stamping each electronic pulse. The data acquired in list-mode included coincidence and anticoincidence events consisting of records of energy and timestamp from primary and guard detectors. Every event was stored in a text file for offline processing and spectral reconstruction. A sophisticated computer simulation was also created with the goals of obtaining a better understanding of the experimental results and calculating efficiency.     

The inhibition of liposaccharide heptosyltransferase WaaC with multivalent glycosylated fullerenes: a new mode of glycosyltransferase inhibition

L,D-Heptosides (L-glycero-D-manno-heptopyranoses) are found in important bacterial glycolipids such as lipopolysaccharide (LPS), the biosynthesis of which is targeted for the development of novel antibacterial agents. This work describes the synthesis of a series of fullerene hexa-adducts bearing 12 copies of peripheral sugars displaying the mannopyranose core structure of bacterial L,D-heptoside. The multimers were assembled through an efficient copper-catalyzed alkyne-azide cycloaddition reaction as the final step. The final fullerene sugar balls were assayed as inhibitors of heptosyltransferase WaaC, the glycosyltransferase catalyzing the incorporation of the first L-heptose into LPS. Interestingly, the inhibition of the final molecules was found in the low micromolar range (IC(50) =7-45 μM), whereas the corresponding monomeric glycosides displayed high micromolar to low millimolar inhibition levels (IC(50) always above 400 μM). When evaluated on a "per-sugar" basis, these inhibition data showed that, in each case, the average affinity of a single glycoside of the fullerenes towards WaaC was significantly enhanced when displayed as a multimer, thus demonstrating an unexpected multivalent effect. To date, such a multivalent mode of inhibition had never been evidenced with glycosyltransferases.