Simultaneous Determination of Pb and Cd Traces in Water Samples by Anodic Stripping Voltammetry Using a Modified GC Electrode

The determination of Pb and Cd with a Nafion‐modified glassy carbon electrode and Cu‐DPABA complex (Cu‐DPABA–NA/GCE; DPABA is methyl 3,5‐bis{bis‐[(pyridin‐2‐yl)methyl]amino}methyl‐benzoate) as an alternative electrode for anodic stripping voltammetry was described. Pb and Cd were accumulated in acetate buffer pH 4 at a potential of ?1.4 V (vs. Ag/AgCl electrode) for 120 s followed by a DPASV scan from ?1.2 to ?0.2 V. Under optimum conditions the calibration curves were linear in the range of 4.8×10^?9–5.0×10^?5 and 5.0×10^?9–5×10^?5 mol L^?1 for Pb and Cd, respectively. Detection limits were 1.8×10^?9 and 1.2×10^?9 mol L^?1 for Pb and Cd, respectively. Different parameters and conditions, such as membrane ingredients, accumulation time, potential and pH value were optimized. A study of interfering substances was also performed. A significant increase in current was achieved at the modified electrode in comparison with the bare glassy carbon electrode. The validation of the proposed method was made by Pb and Cd determination in the certified reference material Groundwater CRM 610 (BCR, Community Bureau of Reference, Brussels, Belgium). The electrode was successfully applied for determination of Pb and Cd in river water with a high content of organic contaminants without any pretreatment.     

Calculation of the Gibbs derivatives on finite Abelian groups through the decision diagrams

Paper considers the calculation of the values of Gibbs derivatives on finite Abelian groups. The calculation procedure is based upon the decision diagram representation of functions defined on finite Abelian groups. Approach permits processing of large functions.     

Oxidation of methyl trimethylsilyl ketene acetals to alpha-hydroxyesters with urea hydrogen peroxide catalyzed by methyltrioxorhenium

In the presence of catalytic amounts of MTO, methyltrioxorhenium, methyl trimethylsilyl ketene acetals are oxidized with urea hydrogen peroxide to afford alpha-hydroxy and alpha-siloxy esters. On treatment with potassium fluoride, the alpha-hydroxy esters are obtained in high yields.     

A general strategy to elisabethane diterpenes: stereocontrolled synthesis of elisapterosin B via oxidative cyclization of an elisabethin precursor

Described is an efficient synthesis of the complex bioactive natural product, elisapterosin B, a potent in vitro inhibitor of Mycobacterium tuberculosis H37Rb. The synthesis elisapterosin B, prepared in its enantiomeric form, proceeds by a highly stereocontrolled sequence commencing with a simple glutamic acid derived compound. Pivotal steps in the sequence include (a) a pinacol-type ketal rearrangement to transfer chirality, (b) an IMDA reaction of an E,Z-diene to construct the elisabethin skeleton, and (c) a biosynthesis-inspired oxidative cyclization of the elisabethin precursor to elisapterosin B.     

Medial efferent effects on auditory-nerve responses to tail-frequency tones II: alteration of phase

It is often assumed that at frequencies in the tuning-curve tail there is a passive, constant coupling of basilar-membrane motion to inner hair cell (IHC) stereocilia. This paper shows changes in the phase of auditory-nerve-fiber (ANF) responses to tail-frequency tones and calls into question whether basilar-membrane-to-IHC coupling is constant. In cat ANFs with characteristic frequencies > or = 10 kHz, efferent effects on the phase of ANF responses to tail-frequency tones were measured. Efferent stimulation caused substantial changes in ANF phase (deltaphi) (range -80 degrees to +60 degrees, average -15 degrees, a phase lag) with the largest changes at sound levels near threshold and 3-4 octaves below characteristic frequency (CF). At these tail frequencies, efferent stimulation had much less effect on the phase of the cochlear microphonic (CM) than on ANF phase. Thus, since CM is synchronous with basilar-membrane motion for low-frequency stimuli in the cochlear base, the efferent-induced change in ANF phase is unlikely to be due entirely to a change in basilar-membrane phase. At tail frequencies, ANF phase changed with sound level (often by 90 degrees-180 degrees) and the deltaphi from a fiber was positively correlated with the slope of its phase-versus-sound-level function at the same frequency, as if deltaphi were caused by a 2-4 dB increase in sound level. This correlation suggests that the processes that produce the change in ANF phase with sound level at tail frequencies are also involved in producing deltaphi. It is hypothesized that both efferent stimulation and increases in sound level produce similar phase changes because they both produce a similar mix of cochlear vibrational modes.     

Development and validation of a new RP-HPLC method for determination of quercetin in green tea

Green tea (Camellia sinensis) contains quercetin as a bioactive compound. Quercetin has anti-inflammatory and anticancer effects. The aim of this paper was to develop and validate an RP-HPLC method for determination of quercetin in green tea simpler and faster than other available methods. RP-HPLC analysis was performed by isocratic elution with a flow rate of 1.0 mL/min. Pure methanol was used as a mobile phase, while the quantification was effected at 370 nm. The separation was performed at 35°C using a C₁₈ column (4.6 × 250 mm, 5 μm). The results showed that the peak area response is linear within the concentration range of 10–70 μg/mL (r = 0.9986). The values of LOD and LOQ were 1.2 and 4 μg/mL, respectively. For the intra-day and intra-instrument reproducibility, RSD were in the range of 0.05–0.84% and 0.89–1.55%, respectively. The results of accuracy for the different concentrations of quercetin (40, 50 and 60 μg/mL) were 101.3, 98.4, and 98.2%. The developed and validated method was successfully applied to the determination of quercetin in green tea extract.     

Plasma electrochemistry: electroreduction in a flame

The manipulation of electron transfer reactions at surfaces forms the cornerstone of electrodeposition and processing of materials on substrates with precise control of stoichiometry and oxidation state. However, the utility of this technique, which is mainly carried out in liquid electrolytes, is ultimately limited by the electrolysis of the solvent which limits a potential window to at best 4.8 V in nonaqueous solutions (A. J. Bard and L. R. Faulkner, Electrochemical Methods: Fundamentals and Applications, Wiley, New York, NY, 2nd edn, 2001; ref. 1) and can be up to 6 V in ionic liquids (A. P. Abbott, K. J. McKenzie, Phys. Chem. Chem. Phys., 2006, 8, 4265-4279; ref. 2). A long-sought-after goal has been to develop a corresponding technique at the solid/gas interface in the absence of a solvent which will allow in principle a potential window in excess of 100 V (J. M. Goodings, J. Guo, A. N. Hayhurst and S. G. Taylor, Int. J. Mass Spectrom., 2001, 206, 137-151; ref. 3). This extended potential window will enable chemistry at the solid/gas interface that is not possible at the solid/liquid interface. Here we describe a new approach to gas-phase electrochemistry using a flame plasma as the electrolyte medium. We demonstrate the controlled electrochemical reduction of Cu(+) to Cu(0) at an electrode surface in a flame environment with resulting deposition of either Cu(2)O or Cu species on conducting diamond electrodes. This approach is novel in that it involves the application of an electrochemical potential difference to change the redox state of surface confined species, not the measurement of flame bore ions (as in flame ionisation detectors). This new technique will permit deposition of films and particles on surfaces with control over the oxidation state of the species. This will provide a valuable enhancement to the capabilities of materials preparation methods such as flame spray deposition.