Microdetermination of carbon in compounds containing alkali metals

Zusammenfassung Wenn organische Verbindungen außer Alkalimetallen auch noch eine zumindest äquivalente Menge Schwefel enthalten, so besteht der Verbrennungsrückstand aus Alkalisulfat. Auf Grund dieser Beobachtung wird darauf hingewiesen, daß sich außer Kaliumdichromat und Vanadiumpentoxyd auch Kaliumpersulfat als oxydierender Zusatz zur organischen Substanz für die Verdrängung des Kohlendioxyds aus der Asche eignet.

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Résumé Quand des composés organiques, outre les métaux alcalins contiennent encore une quantité au moins équivalente de soufre, le résidu de la combustion apparaît sous la forme de sulfate alcalin. Sur la base de cette observation, on a montré, qu'à côté du bichromate de potassium et de l'anhydride vanadique, le persulfate de potassium convenait comme oxydant de la substance organique et pour débarrasser les cendres de l'anhydride carbonique.

     

Electrochemical detection of amino acids at carbon nanotube and nickel-carbon nanotube modified electrodes

The oxidation and enhanced detection of traditionally 'non-electroactive' amino acids at a single-wall carbon nanotube (SWNT) surface and at a nickel hydroxide film electrochemically deposited and generated upon the SWNT layer is reported. Different CNT are compared, with Nafion-dispersed SWNT offering the most favorable layer for constant-potential amperometric detection. Factors affecting the oxidation process, including the pH or applied potential, are assessed. The response of the SWNT-Nafion coated electrode compares favorably with that of copper and nickel disk electrodes under flow injection analysis (FIA) conditions. The electrodeposition of nickel onto the SWNT-Nafion layer (Ni-CNT) led to a dramatic enhancement of the analytical response (vs. that observed at the SWNT or nickel electrodes alone). The oxidative process at the Ni(OH)(2) layer has been studied and the increase in sensitivity rationalized. In the presence of amino acid the Ni-CNT layer undergoes an electrocatalytic process in which the amino acid reduces the newly formed NiO(OH) species. Furthermore, the attractive response of both the CNT and Ni-CNT layers has allowed these electrodes to be used for constant-potential FIA of various amino acids and indicates great promise for monitoring chromatographic effluents. Once again an improved signal was observed at the Ni-CNT electrode compared to nickel deposited upon a bare glassy carbon electrode (Ni-GC).     

Noncovalent attachment of pyro-pheophorbide a to a carbon nanotube

Pyrene mediated noncovalent attachment of a chlorophyll derivative, pyro-pheophorbide a, to a soluble single wall carbon nanotube is reported and the resultant CD, UV-Vis absorbance, fluorescence and 1H NMR spectra are discussed.     

Determination of trace metals by anodic stripping voltammetry using a bismuth-modified carbon nanotube electrode

A bismuth-modified carbon nanotube electrode (Bi-CNT electrode) was employed for the determination of trace lead, cadmium and zinc. Bismuth film was prepared by in situ plating of bismuth onto the screen-printed CNT electrode. Operational parameters such as preconcentration potential, bismuth concentration, preconcentration time and rotation speed during preconcentration were optimized for the purpose of determining trace metals in 0.1M acetate buffer solution (pH 4.5). The simultaneous determination of lead, cadmium and zinc was performed by square wave anodic stripping voltammetry. The Bi-CNT electrode presented well-defined, reproducible and sharp stripping signals. The peak current response increased linearly with the metal concentration in a range of 2-100 microg/L. The limit of detection was 1.3 microg/L for lead, 0.7 microg/L for cadmium and 12 microg/L for zinc (S/N=3). The Bi-CNT electrode was successfully applicable to analysis of trace metals in real environments.     

Tungsten oxide bronzes with alkali metals

Single-phase samples of tungsten bronzes M _x WO₃ (M = K⁺, Rb⁺, Cs⁺) are prepared by solid-state synthesis. The reversibility of the M_0.33WO₃/M⁺-solid electrolyte interface is studied subject to the alkali metal nature and humidity over a wide temperature interval. The exchange current density at 24°C and 58%-relative humidity is 3.6 × 10^?4 A/cm² for the Rb_0.33WO₃/Rb⁺-solid electrolyte interface; 2.2 × 10^?4 A/cm² for the Cs_0.33WO₃/Cs⁺-solid electrolyte interface; and 1.3 × 10^?4 A/cm² for the K_0.33WO₃/K⁺-solid electrolyte interface. A correlation between the reversibility of the bronze|solid electrolyte interface, which is characterized by the exchange current density, and the rate of potential equilibration in sensor systems, where the bronze is a reference electrode, is revealed. Ionic component of the conductivity of the synthesized tungsten oxide bronzes is measured at a background of the predominant electronic conductivity. The ionic conductivity is three orders of magnitude lower than the electronic conductivity; it decreases in the series Rb_0.33WO₃ > Cs_0.33WO₃ > K_0.33WO₃, amounting to 2.3 × 10^?2, 2.1 × 10^?3, and 2 × 10^?4 S cm^?1, respectively. The working capacity of the M_0.3WO₃ bronzes as reference electrodes in sensor systems for carbon dioxide detection is evaluated. The plots of the cell potential vs. the CO₂ concentration in the electrochemical cells are linear, their slopes (59 ± 1 mV/decade) are characteristic for one-electron process. The fastest response to changes in the CO₂ concentration was obtained with the sensor system that used Rb_0.33WO₃ as reference electrode.     

Chiral response of single walled carbon nanotube based sensors to adsorption of amino acids: a theoretical model

Calculations of the interaction energy and dielectric responses of chiral single walled carbon nanotubes to the presence of amino acid enantiomers are carried out. A theoretical study is developed to show that the frequency shifts of selected nanotubes conveniently tailored to the size of the probed molecules and used in a resonator configuration can selectively detect different species of amino acids and the left- and right-handed enantiomers of these species. Criteria for an optimization of the adsorption energy and frequency response on the size and chiral angle of the nanotubes are given. It is found that a very small set of carbon tubes obeys these conditions.     

Micelle-encapsulated carbon nanotubes: a route to nanotube composites

We report a general approach toward dispersing single-walled carbon nanotubes (SWNTs) in solvents and polymer materials, by encapsulating SWNTs within cross-linked micelles. Micelles made from polystyrene-block-poly(acrylic acid) (PS-b-PAA), an amphiphilic block copolymer, are first assembled around SWNTs by gradually adding H2O to a suspension of nanotubes in dimethylformamide. The hydrophilic, outer shells of these micelles are then chemically cross-linked with a difunctional linker molecule. Pure encapsulated SWNTs (e-SWNTs) can then be separated from empty cross-linked micelles by consecutive cycles of centrifugation and redispersion. Atomic force and transmission electron microscopies of the resulting nanostructures demonstrate that individual nanotubes (rather than bundles) have been completely encased in polymer shells whose thickness is slightly larger than that of empty micelles. e-SWNTs encapsulated in PS-b-PAA can be permanently redispersed in H2O, in organic solvents, and in both hydrophobic and hydrophilic polymer matrices with minimal sonication. Micelle encapsulation could improve the compositing of SWNTs in a wide variety of polymer materials for structural, electronic, and thermal applications.     

Formation of ice nanotube with hydrophobic guests inside carbon nanotube

A composite ice nanotube inside a carbon nanotube has been explored by molecular-dynamics and grand canonical Monte Carlo simulations. It is made from an octagonal ice nanotube whose hollow space contains hydrophobic guest molecules such as neon, argon, and methane. It is shown that the attractive interaction of the guest molecules stabilizes the ice nanotube. The guest occupancy of the hollow space is calculated by the same method as applied to clathrate hydrates.     

Electron impact mass spectra of some salts of carboxylic acids with alkali (group Ia) metals

Thirteen of the salts of the alkali metals (Li, Na, K, Rb, Cs) with acetic, 2,2-dimethylpropionic, trifluoroacetic and heptafluorobutyric acid have been found to be sufficiently volatile to give mass spectra under normal electron impact conditions. The metal containing ions observed include (M=metal): [M]⁺, [MO]⁺, [MCO₂]⁺, [M₂]^+·, [M₂O]^+·, [M₂CO₂]^+· and the cluster ions [M_n (carboxylate)_n-1]⁺ for n = 2–8.     

Complex-forming and selectivity properties of substituted tetraphenylethylenediphosphine dioxides with respect to alkali metal cations

The complex-forming reactivity of mono- and disubstituted ethylenediphosphine dioxides of the general formula Ph₂P(O)CH₂C(R¹R²)P(O)Ph₂, and of a tetraphosphorylated monopodand, ortho-bis[4,5-bis(diphenylphosphinyl)-pentoxy]benzene, relative to alkali metal cations have been determined conductometrically in THF-CHCl₃ medium (4:1). Introduction of alkyl substituants in the ethylene bridge of tetraphenylethylenediphosphine dioxide increases its Li/Na selectivity; maximum Li/Na selectivity equal to 40 is observed for the dimethyl-substituted tetraphenylethylenediphosphine dioxide derivative. Among the ligands examined herein the hexadentate tetraphosphoryl-containing monopodand ortho-bis[4,5-bis(diphenylphosphinyl)pentoxy]benzene was found to be the most effective complex-forming agent with respect to lithium (log=6.0), with a high Li/Na selectivity value equal to 40. The syntheses of 1,1-dimethyltetraphenylethylenediphosphine dioxide and of ortho-bis[4,5-bis(diphenylphosphinyl)pentoxy]benzene are described.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 873–877, April, 1990.The authors wish to thank Z. N. Vostroknutovii for carrying out the stability constant measurements in anhydrous acetonitrile.     

Lattice dynamics of carbon chain inside a carbon nanotube

Based on the density functional theory, we obtain the optimum geometry of carbon chain inside a carbon nanotube. The phonon spectrum and specific heat of such a chain and nanotube hybrid system are calculated in terms of lattice dynamics theory. Some new phonon branches that have been obtained come from the coupling vibrations of the nanotube and the chain. The bending and stretching modes of the chain appear at about 520 cm(-1)and 1935 cm(-1) at Gamma point, respectively. It is found that the softening of G modes results mainly from the chain induced variations in the bond length on nanotube, independent of van der Waals interaction, while the stiffening of radial breathing mode is developed by the competition between the two factors. In the low-frequency region, the vibrational density of states are very different from that of the bare nanotube. Its specific heat implies the underlying quantized phonon structures and much large thermal conductivity in the hybrid system. In addition, the chain-length dependent vibration modes are calculated, from which it is expected that a finite chain of about 14 carbon atoms in the nanotube may produce the experimental Raman peak at about 1850 cm(-1).     

Sorption capacity of acetylacetonated humin-like compounds with respect to cations of heavy metals

A method of synthesis of acetylacetonated humin-like compounds was developed. The effect of modification on the sorption capacity of humin-like compounds with respect to heavy metals was studied.     

Peroxidase activity of enzymes bound to the ends of single-wall carbon nanotube forest electrodes

This communication reports the first example, to our knowledge, of enzymes covalently attached onto the ends of vertically oriented single-wall carbon nanotube (SWNT) forest arrays used as electrodes. Quasi-reversible Fe^III/Fe^II voltammetry was observed for the iron heme enzymes myoglobin and horseradish peroxidase coupled to carboxylated ends of the nanotube forests by amide linkages. Results suggest that the “trees” in the nanotube forest behaved electrically similar to a metal, conducting electrons from the external circuit to the redox sites of the enzymes. Electrochemically manifested peroxidase activity of myoglobin and horseradish peroxidase attached to the SWNT forests was demonstrated, with detection limits for hydrogen peroxide in buffer solutions of ∼100 nM. These prototype SWNT-forest biosensors are easy to prepare, and enzyme layers were stable for weeks.     

Characterization of Pd/TiO2 embedded in multi-walled carbon nanotube catalyst with a high photocatalytic activity

Pd particles loading on TiO₂-embedded multi-walled carbon nanotubes (MWCNTs), MWCNTs, and TiO₂ particles were prepared via an impregnation method with palladium(II) chlorate solution followed by heat treatment at high temperature. To characterize the catalysts, BET surface area, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy dispersive X-ray, Fourier transform infrared spectroscopy and ultraviolet-visible spectroscopy were employed. The prepared catalysts were tested in degradation of methyl orange under visible light. Pd/TiO₂-MWCNTs catalyst demonstrates the highest photocatalytic activity, and the phase transformation from PdO to Pd0 phase takes place at heat treatment of embedded TiO₂. The nanoparticles size of TiO₂ can be decreased by introduction of MWCNTs species. Combining structural characterization with kinetic study results we could conclude that the superior catalytic performance could arise due to the Pd/TiO₂-MWCNTs catalyst’s structure.     

Non-functionalized carbon nanotube binding with hemoglobin

Carbon nanotube has a high potential to be used as a biosensor and drug carrier. However, its binding behavior with proteins needs to be studied before the full potential of carbon nanotube in biological studies can be realized. Although many studies have been conducted to characterize the affinity of functionalized carbon nanotube to various types of proteins, our present study for the first time reported that hemoglobin can bind with non-functionalized carbon nanotube, and this binding can be identified by Raman spectrum. Further, this binding has not changed Raman luminescence with specific excitation and emission wavelengths. The immediate application of these findings is to use non-functionalized carbon nanotube as a biosensor to measure H(2)S in blood in which hemoglobin takes about 37% of the total blood volume. Other potential uses of non-functionalized carbon nanotube to bind selective groups of proteins are also hinted.