Quantitative electrochemical formation of phosphotungstate heteropolyanion blues

The optical and ESR spectra of electrochemically reduced phosphotungstate and polyphosphotungstate anions in phosphoric acid were examined as quantitative functions of W⁵⁺ concentration. The optical spectra obey Beer-Lambert laws and are similar to the spectra of reduced silicotungstate anions, indicating the secondary nature of the central cluster in the keggin structure with regard to interactions with the reduction electron. ESR spectra indicate an equivalent correspondence for the W⁵⁺ concentration and unpaired spins for the reduced polyphosphotungstate anion but for the reduced phosphotungstate anion monomer the unpaired spin concentration estimated by ESR was much lower than the W⁵⁺ concentration. Reacting reduced phosphotungstate anions with oxygen showed a I-electron reduction of the oxygen molecule with concomitant oxidation of W⁵⁺ to W⁶⁺ and possibly production of high-molecular-weight, polyanion clusters.     

Coordination compounds of indium : XXXVI. The direct electrochemical synthesis of neutral and anionic organoindium halides

The electrochemical oxidation of indium metal in cells of the type leads to the formation of RInX₂ compounds; if 2,2′-bipyridine is also present, the products are the adducts RInX₂·bipy (R = CH₃, C₂H₅, C₆H₅, C₆H₅CH₂, C₆F₅; X = Cl, Br, I (not all combinations)). When R′₄NX is present instead of bipy, the products are the salts R′₄N[RInX₃]. The electrochemical oxidation apparently proceeds via the general mechanism discussed previously. Anomalous results with CH₃I or C₂H₅I are discussed in the light of the known solution chemistry of organoindium(III) compounds.     

Critical evaluation of additivity schemes for estimating heats of atomization

Additivity schemes for estimating heats of formation and heats of atomization of alkanes and halo- alkanes are scrutinized. A least squares analysis of the heats of atomization of alkanes leads to a revision of the values of the parameters. The improvement in the estimated heats of atomization over the values obtained with parameters previously suggested amounts to at least 100%. The reasons for the deviations from the experimental values are discussed. These parameters can be transfered to haloalkanes. Additional parameters necessary for estimating heats of atomization of haloalkanes are also obtained through least squares analyses.     

Use of Lanthanide‐Containing Polyoxometalates to Sensitise the Emission of Fluorescent Labelled Serum Albumin

Monitoring the interaction of biomolecules is important, and the use of energy transfer is a principal technique in elucidating nanoscale interactions. Lanthanide compounds are promising luminescent probes for biological samples as their emission is longer‐lived than any native autofluorescence. Polyoxometalates (POMs) are interesting structural motifs to incorporate lanthanides, offering low toxicity and a size pertinent for biological applications. Here, we employ iso‐structured POMs containing either terbium or europium and assess their interaction with serum albumin by sensitisation of a fluorescent tag on the protein via LRET (luminescence resonance energy transfer) by exciting the lanthanide. Time‐resolved measurements showed energy transfer with an efficiency of over 90 % for the POM–protein systems. The Tb–POM results were relatively straightforward, while those with the iso‐structured Eu–POM were complicated by the effect of protein shielding from the aqueous environment.     

Influence of anchored cerium ions on the dispersity and activity of Pd/SiO2 catalysts

(Pd+Ce)/SiO₂ catalysts prepared by decomposition of organometallic complexes of Ce and Pd have higher activity, dispersity and selectivity in methanol synthesis than Pd/SiO₂ catalysts.

---

, (Pd+Ce)/SiO₂ , Ce Pd, Pd/SiO₂.

     

Preparation, characterization, surface modification and redox reactions of silver nanoparticles in the presence of tryptophan

The synthesis and characterization of water-soluble dispersions of Ag nanoparticles by the reduction of AgNO(3) using tryptophan under alkaline synthesis conditions are reported. The Ag nanoparticle formation was very slow at low concentration and rapid at extremes. For surface modification and redox reactions, manipulating the interparticles interaction controlled the size of Ag nanoparticles aggregates. Our results suggest that the replacement of the BH(4)(-) ions adsorbed on the nanoparticle surface by tryptophan destabilizes the particles and further caused aggregation. A mechanism is proposed for the formation of silver nanoparticles by tryptophan. The experimental results are supported by theoretical calculations. The Ag nanoparticles were characterized by UV-vis absorption, dynamic light scattering and transmission electron microscopy techniques.     

Atomic layer deposition α-Al2O3 diffusion barriers to eliminate the memory effect in beta-gamma radioxenon detectors

Well designed scintillator detectors, including such examples as ARSA, SAUNA, and XIA’s “PhosWatch”, can readily achieve the state of the art radioxenon detection limits required for nuclear explosion monitoring. They are also reliable, robust detectors that do not require cryogenic cooling for operation. All three employ the principle of beta-gamma coincidence detection to reduce background counting rates, using a BC-404 plastic scintillator to detect the betas and a CsI or NaI scintillator to detect the gamma-rays. As a consequence of this commonality of design, all three also display a “memory effect” arising from the diffusion of Xe into BC-404. Thus, when one sample is pumped out of the detector, a fraction remains behind, embedded in the BC-404, where it artificially raises the signal counting rate for the next sample. While this is not a fatal flaw in scintillator detectors, developing a method to eliminate the memory effect would significantly enhance their utility. This paper reports efforts to develop thin, amorphous Al₂O₃ films, deposited by atomic layer deposition (ALD) to act as diffusion barriers on the BC-404 surfaces exposed to radioxenon. Using radon as a convenient substitute for Xe, film thicknesses between 2 and 10 nm were originally investigated and found to show a memory effect to varying degrees. A second set of 20 and 30 nm films was then produced, which appeared to completely eliminate the radon memory effect, but, when consequentially tested with radioxenon, were found to exhibit xenon memory effects that were approximately half of the effect found on uncoated BC-404. We draw two conclusions from this result. The first is that it will be necessary to develop an improved method for depositing thicker ALD Al₂O₃ films at lower temperatures while still retaining high film quality. The second is that, since xenon is required to test for the xenon memory effect, we need a test method that does not require xenon radio-isotopes in order to facilitate screening large numbers of samples.