CpCo(dithiolene) complexes of highly flexible oxddt ligand with two different Z-shaped and U-shaped structures

[CpCo(oxddt)] complex (2, oxddt = o-xylenediyldithioethylene-1,2-dithiolate, Cp = η⁵-cyclopentadienyl) was obtained from o-xylenediyldithioethylene-1,3-dithiol-2-one (OC(oxddt)) (1). 2 further reacted with diazoalkanes (N₂CHR) to form some alkylidene-bridged adducts [CpCo(CHR)(oxddt)] (R = H (3a), SiMe₃ (3b)). Adduct 3a further reacted with protic acids (HX) to give some S-methylated adducts [CpCo(X)(oxddt)(S-Me)] (X = Cl (4a), OCOCF₃ (4c)), followed by the Co-C bond cleavage in the three-membered cobaltathiirane ring. Two different Z-shaped and U-shaped molecular structures were observed by X-ray diffraction studies. In the former structure (Z), the dithiolene and o-xylylene planes are located at almost parallel position each other, and in the latter structure (U), both planes are not parallel but the o-xylylene moiety is located closer to the dithiolene plane than the Z-shaped one. The Z-shaped structure involves 1 and 2. The U-shaped structure involves 3a, 3b, 4a and 4c. Complex 1 showed a one-dimensional chain through intermolecular π-π interaction in the crystal. Complex 2 had a dimeric interaction between dithioethylenedithiolate moieties (S₂C₂S₂) in the oxddt. The SiMe₃ group in 3b was placed at an exo-position with respect to the cobaltadithiolene ring due to a steric hindrance from the U-shaped oxddt ligand. In 4a, the X and Me groups are located at the opposite side of the dithiolene plane (anti-form) but in 4c, both groups are presented at the same side of the dithiolene plane (syn-form). The NMR analysis of 4a in solution indicated existence of both anti- and syn-isomers (7:1).     

A comparison of new techniques for the detection and determination of triazine herbicides,separated by thin-layer chromatography

Summary A simple, rapid and non-destructive technique has been devised for the detection of triazine herbicides by making use of the fluorescence inhibition properties of such compounds on fluorescing silica gel layers. The sensitivity of this method has been found to be increased up to 20 times in comparison to conventional spray techniques and approaches the detection limits obtained by radiochemical methods.

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Zusammenfassung Ein einfaches, rasches, ohne Zerstörung der Probe durchführbares Verfahren zum Nachweis von Triazin-Herbiziden beruht auf deren Eigenschaft, die Fluoreszenz von Silicagelschichten zu löschen. Die Empfindlichkeit dieses Nachweisverfahrens ist bis zu 20mal besser als die üblicher Sprühverfahren und kommt damit rdiochemischen Methoden nahe.

     

Thermal decomposition of butylindium thiolates and preparation of indium sulfide powders

Thermal properties of organoindium thiolates were investigated by means of thermogravimetric (TG) and differential thermal (DT) analysis. Dibutyl-indium propylthiolates (Buⁿ₂InSPrⁿ, Buⁿ₂InSPrⁱ, Buⁱ₂InSPrⁿ and Buⁱ₂InSPrⁱ) decomposed up to 280°C along with an exothermic DT peak and gave indium(I) sulfide (InS) powders. Although the arylthiolate Buⁿ₂InSPh also afforded InS powders, it decomposed at a slightly higher temperature. In contrast, the dithiolate and the dithiocarbamate complexes [BuⁿIn(SPrⁱ)₂ and In (S₂CNBu₂)₃] gave indium(III) sulfide (In₂S₃) powders.     

Explosion hazards of ion exchange resin mixed with perchloric acid

On January 21, 2003, an explosion occurred while ion exchange resin (IER) was being used to separate impurities from uranium solution. To clarify the cause of the accident and go/no-go criteria of the explosion, elemental analysis of the IER, DSC analysis, and SIKAREX analysis (a screening tool for runaway reactions) were performed. Finally, experiments on the same scale as the accident were conducted in an explosion chamber. When HClO₄ was added to IER-NO₃, the IER violently exploded without any heating nor metal ions such as uranium. It was confirmed that the accident was caused by an incorrect procedure in the chemical process. From the standpoint of explosion safety, IER-NO₃ in particular should be kept away from perchloric acid in the laboratory.     

Behaviour in solution of piezoelectric quartz crystals coated with poly(vinylpyridines). Application to the determination of copper(II)

Poly(2-vinylpyridine) or poly(4-vinylpyridine) coated on a piezoelectric quartz crystal adsorbed copper, thus decreasing the oscillation frequency. The bound copper could be removed by EDTA solution. Poly(4-vinylpyridine) is recommended to determine copper (5–35 μM) in a maleate buffer at pH 6.6 flowing over the coated crystal for 5 min. Iron(III) and cadmium interfered.     

Observation and evaluation of proton diffusion in porous media by the pH-imaging microscope using a flat semiconductor pH sensor.

The diffusion of protons in porous media was observed and evaluated using a pH-imaging microscope with a flat semiconductor. Small particles were packed on the sensing surface of the flat sensor, followed by the addition of a lactic acid droplet on the top of the packed particle layer. The pH distribution accompanied by the diffusion of lactic acid was visualized at the bottom of the layer using the flat sensor. The difference in the diffusion property was confirmed depending on the particle type. The effective diffusion coefficients of the lactic acid in some porous media were estimated by combining the experimental results and mathematical calculation.     

Efficient optical near-field energy transfer along an Au nanodot coupler with size-dependent resonance

We confirmed that the light intensity (λ=785 nm) scattered from an isolated hemispherical Au nanoparticle was resonantly enhanced at a diameter of 200 nm and a height of 50 nm, as observed experimentally using a collection-mode near-field optical microscope. The experimental results agreed with the calculated results using Mie’s theory. Furthermore, we observed resonant energy transfer of the optical near-field energy along a chain of Au nanoparticles. The magnitude of the transferred energy increased resonantly at the size of resonant light scattering for an isolated Au nanoparticle (200 nm diameter with 240 nm center-to-center separation). PACS 42.82.Et; 73.20.Mf; 78.67.Bf     

On embedding problems with restricted ramifications

Archiv der Mathematik - Let L / k be a Galois extension with Galois group G, and $(varepsilon ): 1to Ato Eto Gto 1$ a central extension. We study the existence of the Galois extension M / L /...     

Development of health monitoring method for pecan nut trees using side video data and computer vision

Optical Review - Increasing efficiency and productivity in the field of agriculture is important to provide sufficient food to the world’s increasing population. It is important to monitor...     

Large four-wave mixing of spatially extended excitonic states in thin GaAs layers

We study the size dependence of the nonlinear response of weakly confined excitons for the size region beyond the long wavelength approximation regime. The observed degenerate-four-wave mixing signal of GaAs thin layers exhibits an anomalous size dependence, where the signal is resonantly enhanced at a particular thickness region. The theoretical analysis elucidates that this enhancement is due to the size-resonant enhancement of the internal field with a spatial structure relevant to the nondipole-type excitonic state. These results establish the formerly proposed new type of size dependence of nonlinear response due to the nonlocality induced double resonance.