Direct current conduction in ammonium perchlorate single crystals

The dc electrical conductivity of pure and doped ammonium perchlorate (AP) has been studied in two different crystal orientations, with the electric field applied perpendicularly to either (001) or (210) planes. The conductivity along the direction of the c axis was found to be lower than that normal to (210) by a factor of 5 to 10. The dc electrical conductivity of AP is decreased by Pb²⁺ ions but increased by SO^2?₄ and CrO^2?₄ ions. The conductivity of pure AP and of Pb²⁺-doped AP displays two regions with activation energies for conduction of 0.56 and 0.87 eV, respectively. The conductivity of the anion-doped crystals has a single activation energy, 0.66 eV for SO^2?₄ and 0.72 eV for CrO^2?₄. Exposure to ammonia enhances the conductivity of pure AP. A proton conduction mechanism is proposed that takes due regard of the structure of AP. The effect of the various additives on the conductivity are attributed to their influences on the formation of charge-carrying protons.     

Development of electrochemical processes for nitrene generation and transfer

An electrochemical strategy for running nitrogen-transfer reactions on chemically inert anode surfaces has been developed. The generation and trapping of highly reactive nitrene-transfer reagents can be accomplished under mild conditions on platinum electrodes. The key factor that accounts for the high levels of chemoselectivity in this process is the phenomenon of overpotential. We have found that molecules that are similar in terms of propensity toward oxidation can be differentiated on the basis of their affinity to a given electrode surface. Thereby, reactive species can be selectively generated in the presence of acceptor molecules of interest. Specifically, a wide range of structurally dissimilar olefins can be transformed into the corresponding aziridines in the presence of N-aminophthalimide. Likewise, nitrene generation in the presence of sulfoxides leads to their chemoselective transformation into the corresponding sulfoximines. In this paper we discuss the underlying mechanistic foundation of these reactions.     

195Pt-NMR. Spectroscopy. The direct measurement of the values 1J (195Pt, 14N) and chemical shift data for the complexes trans-[PtCl2(C2H4) (substituted pyridine)]

The values ⁿJ (¹⁹⁵Pt, ¹⁴N) are shown to be measurable directly from the ¹⁹⁵Pt spectrum for a variety of complexes containing nitrogen ligands. The sample temperature can play an important role in determining the width of the ¹⁹⁵Pt signal. ¹⁹⁵Pt chemical shifts for the complexes trans-[PtCl₂(C₂H₄) (substituted pyridine)] have been measured. Methyl substitution at the 2- and 6-positions produces a relatively large downfield shift.     

Negative ion atmospheric pressure ionization mass spectrometry: Ionization of aromatic hydrocarbons

A corona discharge atmospheric pressure ionization source generates the reagent ions, OH^? and O^? ions in addition to better known O₂^? ions, when ambient air is used as the carrier. All three ions are gas-phase bases that could form negative ions from organics via proton abstraction. Ionization of simple aromatic hydrocarbons by O₂^? is thermodynamically not feasible. Simple aromatic hydrocarbons are ionized only by O^? and/or OH^? to form [M ? H]^? ions. However, [M ? H]^? ions do not appear in the mass spectrum as they undergo stabilization via clustering with predominantly oxygen atoms.     

Isolation of palm tocols using supercritical fluid chromatography

Crude palm oil contains 600 to 1000 ppm of tocols in the form of tocopherols and tocotrienols. These palm tocols have been isolated and analyzed in the past by various chromatographic techniques such as open column chromatography, high-performance liquid chromatography, as well as thin-layer chromatography. Supercritical fluid chromatography (SFC) has emerged as a more advanced chromatographic technique in recent years. The tocols present in palm oil are successfully isolated using SFC. Identification of these tocols is supported by various spectroscopic techniques such as 1H NMR, 13C NMR, and mass spectrometry.     

Multiply charged ions in ionspray tandem mass spectrometry

Multiply charged anions of some 30 species containing multiple carboxylic, sulphonic and/or phosphoric groups generated by ionspray were studied by using tandem mass spectrometry (MS/MS). Two trends emerged: (1) lower-charged ions are preferentially evaporated, and (2) for more highly charged ions, evaporability is a function of ion size. Triply and quadruply charged ions were observed for azo dyes with molecular masses in the 700-900 Dalton range. Daughter-ion mass spectra of selected multiply charged ions are presented.     

Hydrothermal Realization of a Hierarchical,Flowerlike MnWO4@MWCNTs Nanocomposite with Enhanced Reversible Li Storage as a New Anode Material

A phase‐pure MnWO₄‐based nanocomposite, MnWO₄@MWCNTs (MWCNTs=multiwalled carbon nanotubes), was successfully synthesized through a simple hydrothermal reaction at 180 °C by adjusting the pH of the precursor medium. The resulting nanocomposite maintains the original flowerlike morphology of MnWO₄ with hierarchical structures composed of numerous single‐crystalline nanorods that drive growth preferentially along the [001] direction. The growth mechanism for the flowerlike formations is also discussed. In addition, the Li electroactivity of pure MnWO₄ and MnWO₄@MWCNTs electrodes was investigated. As an anode for Li‐ion batteries, the MnWO₄@MWCNTs nanocomposite showed enhanced electrochemical performance in reversible Li storage relative to that shown by bare MnWO₄ electrodes, including a high capacity of 425 mAh g^?1 and superior rate performance. This performance can be attributed to the synergistic effect of the nanocomposite combined with the MWCNTs, which provide efficient electron transport in their role as a conductor.