Evaluating the electrochemical capacitance of surface-charged nanoparticle oxide coatings

While transition metal oxides have been thoroughly investigated as coatings for electrochemical capacitors due to their pseudocapacitance, little work has been done investigating other oxide coatings. There exists a whole class of nanoporous oxides typically synthesized by sol-gel chemistry techniques that have very high differential capacitance. This high differential capacitance has been attributed to the surface potential of these materials and the close approach of counterions near the surface of these oxides. This study focuses on investigating the electrochemical capacitance of non-transition metal oxide nanoparticle coatings when deposited on supporting electrodes. Here, we show that, by adding coatings of SiO(2), AlOOH, TiO(2), and ZrO(2) nanoparticles to graphite support electrodes, we can increase the electrochemical capacitance. We also show that the measured electrochemical capacitance of these oxide-coated electrodes directly relates to the electrophoretic mobility of these materials with the lowest values in capacitance occurring at or near the respective isoelectric pH (pH(IEP)) of each oxide.     

Chalcogenidobis(ene-1,2-dithiolate)molybdenum(IV) complexes (chalcogenide E = O, S, Se): probing Mo≡E and ene-1,2-dithiolate substituent effects on geometric and electronic structure

New square-pyramidal bis(ene-1,2-dithiolate)MoSe complexes, [Mo(IV)Se(L)(2)](2-), have been synthesised along with their terminal sulfido analogues, [Mo(IV)S(L)(2)](2-), using alkyl (L(C(4)H(8))), phenyl (L(Ph)) and methyl carboxylate (L(COOMe)) substituted dithiolene ligands (L). These complexes now complete three sets of Mo(IV)O, Mo(IV)S and Mo(IV)Se species that are coordinated with identical ene-1,2-dithiolate ligands. The [alkyl substituted Mo(S/Se)(L(C(4)H(8)))(2)](2-) complexes were reported in prior investigations (H. Sugimoto, T. Sakurai, H. Miyake, K. Tanaka and H. Tsukube, Inorg. Chem. 2005, 44, 6927, H. Tano, R. Tajima, H. Miyake, S. Itoh and H. Sugimoto, Inorg. Chem. 2008, 47, 7465). The new series of complexes enable a systematic investigation of terminal chalcogenido and supporting ene-1,2-dithiolate ligand effects on geometric structure, electronic structure, and spectroscopic properties. X-ray crystallographic analysis of these (Et(4)N)(2)[MoEL(2)] (E = terminal chalocogenide) complexes reveals an isostructural Mo centre that adopts a distorted square pyramidal geometry. The M≡E bond distances observed in the crystal structures and the ν(M≡E) vibrational frequencies indicate that these bonds are weakened with an increase in L→Mo electron donation (L(COOMe) < L(Ph) < L(C(4)H(8))), and this order is confirmed by an electrochemical study of the complexes. The (77)Se NMR resonances in MoSeL complexes appear at lower magnetic fields as the selenido ion became less basic from MoSeL(C(4)H(8)), MoSeL(Ph) and MoSeL(COOMe). Electronic absorption and resonance Raman spectroscopies have been used to assign key ligand-field, MLCT, LMCT and intraligand CT bands in complexes that possess the L(COOMe) ligand. The presence of low-energy intraligand CT transition in these MoEL(COOMe) compounds directly probes the electron withdrawing nature of the -COOMe substituents, and this underscores the complex electronic structure of square pyramidal bis(ene-1,2-dithiolate)-Mo(IV) complexes that possess extended dithiolene conjugation.     

Chaos-based communication systems in non-ideal channels

Recently, many chaos-based communication systems have been proposed. They can present the many interesting properties of spread spectrum modulations. Besides, they can represent a low-cost increase in security. However, their major drawback is to have a Bit Error Rate (BER) general performance worse than their conventional counterparts. In this paper, we review some innovative techniques that can be used to make chaos-based communication systems attain lower levels of BER in non-ideal environments. In particular, we succinctly describe techniques to counter the effects of finite bandwidth, additive noise and delay in the communication channel. Although much research is necessary for chaos-based communication competing with conventional techniques, the presented results are auspicious.     

Crosslinking of oligomers bearing carbamoyloxyimino groups with their photochemical and thermal reactions

Carbamoyloxyimino (COI) groups are precursors of photochemically base‐generating groups as well as those of thermally isocyanate‐generating groups. In this study, photochemical and thermal reactions of COI groups in oligomers were investigated by spectral analyses and solubility changes. Oligomers bearing three types of COI groups were prepared. COI groups in all oligomer films were photolyzed on irradiation with 254 nm of light and were deblocked to form isocyanato groups on heating. From the IR spectral analyses, the formation of urea linkage was confirmed by the decrease in isocyanato groups and peak generation because of urea groups on postexposure bake (PEB) treatment. For all oligomer films, PEB was effective for the enhancement of insolubilization of the films in tetrahydrofuran. Heating followed by irradiation was also effective for the insolubilization. These results indicated that photochemical and thermal treatments of COI groups afforded highly sensitive crosslinking systems because of photochemically generated basic groups and thermally generated isocyanato groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2612–2620, 2004     

Biosorption of precious metal ions by chicken feather

Chicken feather (C-feather) is an intricate network of stable and water-insoluble protein fibers with high surface area and is an abundant bioresource. C-feather protein was found to accumulate various precious metal ions (gold and platinum metals) selectively from their dilute aqueous solutions in high yield and in short contact time, depending on pH and characteristics of the individual precious metal ions. Under certain condition, the sequestering level of precious ions, Au(III), Pt(II), and Pd(II) approaches about 17, 13, and 7% of dry wt of C-feather, respectively. Gold(III) potassium cyanade was also accumulated up to 5.5% at pH 2.0. The presence of 100-fold (mol) of coexisting cations, such as Na⁺, Fe(III), Cu(II), and Ni(II), did not show a discernible effect on the precious metal uptake rate and capacity of C-feather. Experiment suggested C-feather is promising for use in the removal/recovery of precious metals as well as water pollution control. A qualitative discussion is given about the excellent adsorption behavior of C-feather.

     

Effect of alcohols on the degradation of crosslinked unsaturated polyester in sub-critical water

The effect of alcohols on the degradation of unsaturated polyesters crosslinked with styrene was studied in sub-critical water at 300 °C. The de-crosslinked polymer was obtained by degradation of polyester chains in sub-critical water, and the de-crosslinking was enhanced by adding alcohols and phenols having a long alkyl chain such as 1-tetradecanol and 3-pentadecylphenol. However, the enhancement was not observed in the presence of diols even when they had a long alkyl chain. This finding suggests that transesterification enhanced the de-crosslinking of the polymer in sub-critical water.     

Practical total syntheses of epiquinamide enantiomers

Short and practical syntheses of epiquinamide and its enantiomer were accomplished with high overall yields and high stereoselectivity from readily available starting materials.     

Volumetric Study of the Interaction Between Chloride Salts and Polyvinylpyrrolidone in Aqueous Solution

We are interested in polyvinylpyrrolidone as an analog for the D-state proteins. In a volumetric study, the interactions between polyvinylpyrrolidone (PVP) and sodium-, potassium-, calcium-, and tetrabutylammonium chloride at 35°C in a series of aqueous PVP solutions over a concentration range of PVP up to 20 wt.% was performed. The volumes of transfer at infinite dilution _tr V ₂ ⁰ from water to the PVP solutions were determined for the salts; their decreasing order showed a parallel relation to the Hoffmeister series. The _tr V ₂ ⁰ data were analyzed by applying the McMillan–Mayer method to obtain the volumetric interaction coefficients between the ions and the polymer unit.