Determination of inorganic arsenic and organic arsenic compounds in marine organisms by hydride generation/cold trap/gas chromatography— mass spectrometry

The behavior of arsenite, methylarsonic acid, dimethylarsinic acid, trimethylarsine oxide, dimethyl-R-arsine oxides, and trimethyl-R-arsonium compounds (R = carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl) toward sodium borohydride and hot aqueous sodium hydroxide was investigated. The arsines obtained by sodium borohydride reduction of the undigested and digested solutions were collected in a liquid-nitrogen cooled trap, separated with a gas chromatograph, and detected with a mass spectrometer in the selected-ion-monitoring mode. The investigated arsenic compounds were stable in hot 2 mol dm^?3 sodium hydroxide except arsenobetaine [trimethyl(carboxymethyl)arsonium zwitterion] that was converted to trimethylarsine oxide, and dimethyl(ribosyl)arsine oxides that were decomposed to dimethylarsinic acid. Hydride generation before and after digestion of extracts from marine organisms allowed inorganic arsenic, methylated arsenic, arsenobetaine, and ribosyl arsenic compounds to be identified and quantified. This method was applied to extracts from shellfish, fish, crustaceans, and seaweeds.     

The branching point in the petasaccharides viridopentaoses A,B and C

The branching point in the viridopentaoses has been determined by a three step sequence, permethylation/methanolysis/benzoylation, followed by CD measurements, a method which can be scaled down to microgram quantities.     

Kinetic studies of the reactions CH2I2 + HI⇄CH3I + I2 and 2 CH3I⇄CH4 + CH2I2 the heat of formation of the iodomethyl radical

The rate of the reaction CH₂I₂ + HI ? CH₃I + I₂ has been followed spectrophotometrically from 201.0 to 311.2°. The rate constant for the reaction fits the equation, log (k₁/M^?1 sec^?1) = 11.45 ± 0.18 - (15.11 ± 0.44)/θ. This value, combined with the assumption that E₂ = 0 ± 1 kcal/mole, leads to ΔH (CH₂I, g) = 55.0 ± 1.6 kcal/mole and DH (H? CH₂I) = 103.8 ± 1.6 kcal/mole. The kinetics of the disproportionation, 2 CH₃I ? CH₄ + CH₂I₂ were studied at 331° and are compatible with the above values.     

Coherent transients observed by Stark switching in ruby having narrow optical hole burning

By using the Stark switching technique we observed new coherent transient signals in ruby at low laser intensities, which are unique in solids where T₁ ? T₂. It was confirmed that the existence of narrow optical hole burning before the switching plays an essential role in giving rise to the signals. The effects of the multiple optical hole burning were also observed in the time domain. Assuming the existence of the holes, the signals can well be interpreted by linear system analysis.     

Assignments of optically pumped CD3OH laser lines

Six FIR laser lines from CD₃OH pumped by the 10R(36) and the 10R(18) CO₂ laser lines are assigned to specific rotational energy levels in the excited C–0 stretch state. It is found that their upper laser levels are shifted by a Fermi resonance between the C–0 stretch vibration and the third and forth harmonics of the torsional mode. The Fermi resonance shifts are +0.332 cm^–1 and +2.251 cm^–1 for the upper laser levels pumped by the 10R(36) and the 10R(18) CO₂ laser lines, respectively. Calculated frequencies of the pump and the laser transitions agree with those of the pump CO₂ laser lines and the observed FIR laser lines within estimated accuracy.     

Studies of phase characteristics of various photon echoes with a phase sensitive detection method

Various optical coherent transient signals in ruby have been examined by using an optical phase sensitive detection (PSD) technique. The PSD is performed by comparing the phase of the heterodyne beat signals obtained by the Stark switching technique with that of a local oscillator whose frequency is equal to the heterodyne beat frequency. The optical FID, two-pulse photon echoes, radiation locked echoes and notched echoes have been detected as υ-mode signals with small u-mode signals probably due to the asymmetry of the inhomogeneous broadening. The dependence of the phase of the radiation locked and notched echoes upon the driving pulses is also examined. The experimental results are in good agreement with theoretical predictions based on Bloch equations.     

Layer-by-layer electrodeposition of copper in the presence of o-phenanthroline, caused by a new type of hidden NDR oscillation with the effective electrode surface area as the key variable

Electrochemical deposition of copper (Cu) from aqueous acidic Cu2+ solutions with o-phenanthroline (o-phen) shows both potential and current oscillations, together with a (partially hidden) N-shaped negative differential resistance (N-NDR), indicating that the oscillations are classified into hidden N-NDR (or HN-NDR) oscillations. The color and the surface morphology of Cu deposits oscillate in synchronization with the potential and current oscillations. Microscopic inspection has shown that dense round Cu leaflets, which look gray, grow in the positive side of the potential oscillation or in the high-current state of the current oscillation, whereas thin Cu leaflets, which look black, grow in the opposite-side stages of the potential and current oscillations, thus finally resulting in a layered Cu deposit with the layer thickness of about 5 microm. The appearance of the NDR is explained to be due to adsorption of the reduced form of a [Cu(II)(o-phen)2]2+ complex, which suppresses the Cu electrodeposition. The increase in the effective electrode surface area by growth of thin Cu leaflets, on the other hand, causes a current increase that can hide the NDR. This NDR-hiding mechanism is of a new type and the present oscillation is regarded as a new-type of HN-NDR oscillator.     

Observation of electrostatically released DNA from gold electrodes with controlled threshold voltages

DNA oligo-nucleotides, localized at Au metal electrodes in aqueous solution, are found to be released when applying a negative bias voltage to the electrode. The release was confirmed by monitoring the intensity of the fluorescence of cyanine dyes (Cy3) linked to the 5' end of the DNA. The threshold voltage of the release changes depending on the kind of linker added to the DNA 3'-terminal. The amount of released DNA depends on the duration of the voltage pulse. Using this technique, we can retain DNA at Au electrodes or Au needles, and release the desired amount of DNA at a precise location in a target. The results suggest that DNA injection into living cells is possible with this method.