Simultaneous multi-element determination of trace metals in sea water by inductively-coupled plasma atomic emission spectrometry after coprecipitation with gallium

Coprecipitation with gallium hydroxide is studied for the preconcentration of trace metals in sea water before multi-element analysis by inductively-coupled plasma/atomic emission spectrometry. Gallium precipitates at pH 9 only when magnesium is present. Optimum conditions are established for multi-element preconcentration and removal of matrix elements. The method is almost free from contamination because of the use of highly pure gallium meetal and only a small amount of sodium hydroxide for pH adjustment. Spectral interferences from gallium are negligible and a concentratioin factor of more than 200 can be obtained. Detection limits range from a few ng l^?1 to 150 ng l^? for Al, Co, Cr, Fe, La, Mn, Ni, Ti, V, Zn, Y and Pb. Artificial and natural sea-water samples can be analyzed with adequate precision.     

Electrostatic Interactions That Determine the Rate of Pseudorotation Processes in Oxyphosphorane Intermediates: Implications with Respect to the Roles of Metal Ions in the Enzymatic Cleavage of RNA

The enzymatic cleavage of RNA takes place via a cyclic pentacoordinate oxyphosphorane intermediate/transition state. We carried out ab initio investigations on the neutral cyclic oxyphosphorane, which exists as a stable intermediate. As a consequence of the conformational preferences of the pentacoordinate trigonal bipyramidal intermediates, the rotation of the P-OH bonds is strongly coupled with the reaction coordinate for the pseudorotation process. In addition, the neutral PF(4)OH species has a higher barrier to pseudorotation than the corresponding anionic species PF(4)O(-). These findings are related to the positive charge of the hydrogen atoms on the equatorial oxygens in the trigonal bipyramidal structures: the hydrogen atoms preferably adopt eclipsed positions relative to the axial ligands. Fixing the cationic species in these regions causes an increase in the barrier heights for pseudorotation processes and, thus, prevents isomerization by pseudorotation. Consequently, metal coordination in the double-metal ion mechanism for enzymatic cleavage of RNA should serve to exclusively stabilize the trigonal bipyramidal intermediate/transition state for the in-line attack and departure process.     

Phosphazene Base tBu-P4 Catalyzed Methoxy–Alkoxy Exchange Reaction on (Hetero)Arenes

The organic superbase tBu-P4 catalyzes methoxy-alkoxy exchange reactions on (hetero)arenes with alcohols. The catalytic reaction proceeded efficiently with electron-deficient methoxy(hetero)arenes as well as with a variety of alcohols, including 3-amino-1-propanol, β-citronellol, menthol, and cholesterol. An intramolecular version of this reaction furnished six- and seven-membered ring compounds.     

Self-Modulation of Scattering Intensity from a Silica Sphere Coated with a Sol-Gel Film Doped with J-Aggregates

A micrometer-sized nonlinear optical resonator constituted of a silica microsphere coated with J-aggregates has been fabricated by the sol-gel process. We determined the scattering light spectrum and discuss the application of the observed effect for the realization of an optical switching element. Optical evaluation of the sphere has been performed in the attenuated-total-reflection (ATR) configuration. We excited a whispering gallery mode and measured the nonlinear ATR signal dependence on excitation intensity. The experimental result agrees very well with the simulation results obtained using the Mie theory and the finite-difference time-domain method taking into account optical Kerr nonlinearity. The permittivity of the film of J-aggregates was measured by ATR method at several wavelengths and the value at the desired wavelength was determined by extrapolation using the Lorentz function.     

Novel High Precision Optoelectronic Device Fabrication Technique Using Guided Fluidic Assembly

High precision assembly of laser diodes (LDs) on silicon wafer substrates for use in advanced optoelectronic devices is an important issue from a mass production point of view. An acceptable alternative to replace an obsolete pick and place flip chip bonding robotic technology with a simple, low cost and high speed technique is desired for industrial applications. We have investigated a novel assembling technique with micrometer order accuracy for LDs and other microchips. Its feasibility for rapidly assembling a large number of high power edge emitting LDs is practically demonstrated. A 150 $mUm thick nickel metal mask is used to confine as well as guide the unassembled LDs into the recesses by its restricted displacements. This technique is based on guiding the LDs within a suitable fluidic medium and the assembling process is performed in two steps: (i) coarse precision with a confinement mask to bring LDs near the recesses to achieve high assembling efficiency and (ii) fine precision due to the electrode patterns on the base surface of LDs, under fluidic as well as gravitational force. The assembly of 80 red LDs of the same size and of 40 pairs of red and infrared LDs of two different sizes is successfully demonstrated within less than ±2 $mUm precision and 100% efficiency in a few seconds after transferring them into a confinement mask region.     

Experimental study on heat transfer of thermally developing and developed, turbulent, horizontal pipe flow of dilute air-solids suspensions

Heat transfer characteristics of a turbulent, dilute air-solids suspension flow in thermally developing/developed regions were experimentally studied, using a uniformly heated, horizontal 54.5 mm-ID pipe and 43-μm-diameter glass beads. The local heat transfer was measured at 27 locations from the inlet to 120-dia downstream of the heated section over a range of Reynolds numbers 3×10⁴−1.2×10⁵ and solids loading ratio 0–3, and the fully developed profiles of air velocity/temperature and particle mass flux were measured at a location 140-dia downstream of the heated section using specially designed probes, inserted into the suspension flow. The effects of the Reynolds number, solids loading ratio, and azimuthal/longitudinal locations on the heat transfer characteristics and their interactions are discussed through comparison of the present results with the data obtained by other investigators. Received on 14 October 1996     

High-resolution characterization of liquid-crystalline [60]fullerenes using solid-state nuclear magnetic resonance spectroscopy

Liquid-crystalline materials containing fullerenes are valuable in the development of supramolecular switches and in solar cell technology. In this study, we characterize the liquid-crystalline and dynamic properties of fullerene-containing thermotropic compounds using solid-state natural abundance (13)C NMR experiments under stationary and magic angle spinning sample conditions. Chemical shifts spectra were measured in isotropic, liquid-crystalline nematic and smectic A and crystalline phases using one-dimensional (13)C experiments, while two-dimensional separated local-field experiments were used to measure the (1)H- (13)C dipolar couplings in mesophases. Chemical shift and dipolar coupling parameters were used to characterize the structure and dynamics of the liquid-crystalline dyads. NMR data of fullerene-containing thermotropic liquid crystals are compared to that of basic mesogenic unit and mesomorphic promoter compounds. Our NMR results suggest that the fullerene-ferrocene dyads form highly dynamic liquid-crystalline phases in which molecules rotate fast around the symmetry axis on the characteristic NMR time scale of approximately 10 (-4) s.     

Ni(0)-promoted hydroxycarboxylation of 1,2-dienes by reaction with CO2 and O2

[structure: see text]. A novel method for the preparation of hydroxy carboxylic acid derivatives has been developed by O2-oxidation of pi-allylnickel intermediates generated by Ni(0)-mediated coupling of 1,2-dienes with CO2.     

Determination of trace iron in indium phosphide wafer by on-line matrix separation and inductively coupled plasma mass spectrometry

A method for the determination of iron in indium phosphide (InP) wafer is proposed. In the present experiment, an on-line matrix separation system using an ion exchange column was combined with inductively coupled plasma mass spectrometry (ICP-MS) for the determination of ng g⁻¹ level of iron. In the on-line matrix separation, indium and iron in the sample solution was passed through a strongly-basic anion exchange resin column with the 9 M HCl carrier solution, where indium was eluted from the column and iron was adsorbed on it. Then, iron was eluted with the carrier solution of 0.3 M HCl containing 1 ng ml⁻¹ cobalt, and it was directly introduced into the ICP-MS nebulizer. In ICP-MS measurement, cobalt in the carrier solution was used as an internal standard to correct the change in sensitivity due to matrix effect, and the peak area integration was performed to quantify iron and cobalt in the integration time range of 20-60 s from the start of the cobalt solution flow. The detection limit (3σ) for iron was 3 ng g⁻¹, and the recoveries for iron in the 0.8, 2.4, and 8.0% indium solutions were almost 100%. The method was applied to the determination of iron in commercially available iron-doped InP wafers. The obtained results for InP wafer samples with the high iron concentration were in good agreement with those obtained by graphite furnace atomic absorption spectrometry (GFAAS).