Electrothermal atomic absorption spectrometric determination of cadmium in environmental samples with niobium wire preconcentration method

A preconcentration method by adsorption of cadmium on a niobium wire was developed for the environmental waters, followed by electrothermal atomic absorption spectrometry with a tungsten tube atomizer. After the preconcentration, the niobium wire was directly inserted into the tungsten tube atomizer. In the preconcentration (adsorption) process of cadmium, the optimal immersing time was 60?s. The effects of large amounts of concomitants on the preconcentration of cadmium were evaluated. When 10³–10⁴ fold excess of matrix elements existed in aqueous solution at pH 4 and 9, the cadmium response was profoundly affected by the matrix elements. However, the cadmium absorption signal was not significantly influenced at pH 7. Therefore, pH 7 was selected for the application into the real environmental samples. Under the optimal conditions, the detection limit (3S/N) for cadmium by the niobium wire preconcentration method was 7.0?pg?mL^?1 and the relative standard deviation was 6.8%. The method with preconcentration on a niobium wire was applied to the determination of cadmium in water and proved to be sensitive, simple and convenient. Because this preconcentration method can be utilized in the in situ treatment of trace cadmium in environmental water samples, it was unnecessary to carry the water samples to the analytical work place. The technique was shown to be useful for the determination of cadmium in environmental water samples at 0.1–1?µg?L^?1 levels.     

Identification of novel EED-EZH2 PPI inhibitors using an in silico fragment mapping method

Journal of Computer-Aided Molecular Design - Enhancer of zeste homolog 2 (EZH2) is a histone lysine methyltransferase that is overexpressed in many cancers. Numerous EZH2 inhibitors have been...     

Induced Fitting and Polarization of a Bromine Molecule in an Electrophilic Inorganic Molecular Cavity and Its Bromination Reactivity

Dodecavanadate, [V₁₂O₃₂]^4? (V12), possesses a 4.4 Å cavity entrance, and the cavity shows unique electrophilicity. Owing to the high polarizability, Br₂ was inserted into V12, inducing the inversion of one of the VO₅ square pyramids to form [V₁₂O₃₂(Br₂)]^4? (V12(Br2)). The inserted Br₂ molecule was polarized and showed a peak at 185 cm^?1 in the IR spectrum. The reaction of V12(Br2) and toluene yielded bromination of toluene at the ring, showing the electrophilicity of the inserted Br₂ molecule. Compound V12(Br2) also reacted with propane, n‐butane, and n‐pentane to give brominated alkanes. Bromination with V12(Br2) showed high selectivity for 3‐bromopentane (64 %) among the monobromopentane products and preferred threo isomer among 2‐,3‐dibromobutane and 2,3‐dibromopenane. The unique inorganic cavity traps Br₂ leading the polarization of the diatomic molecule. Owing to its new reaction field, the trapped Br₂ shows selective functionalization of alkanes.     

Tolerance,bioaccumulation and biotransformation of arsenic in freshwater prawn (Macrobrachium rosenbergii)

Tolerance bioaccumulation and biotransformation of arsenic compounds by a freshwater prawn (Macrobrachium rosenbergii) were investigated. M. rosenbergii was exposed to 10, 20, 30 and 35 μg As cm⁻³ of disodium arsenate [abbreviated as As(V)], 25, 50, 100 and 120 μg As cm⁻³ of methylarsonic acid (MMAA), or 100,200, 300 and 350 μg As cm⁻³ of dimethylarsinic acid (DMAA). Tolerances (50% lethal concentration: LC₅₀) of the prawn against As(V), MMAA, and DMAA were 30, 100, and 300 μg As cm⁻³, respectively. The prawn accumulated arsenic compounds directly from aqueous phase and biotransformed them in part. Both methylation and demethylation of the arsenicals were observed in vivo. Highly methylated and less toxic arsenicals were less accumulated in M. rosenbergii.     

Proton Conduction at High Temperature in High-Symmetry Hydrogen-Bonded Molecular Crystals of RuIII Complexes with Six Imidazole-Imidazolate Ligands

A new H-bonded crystal [Ru^III(Him)₃(Im)₃] with three imidazole (Him) and three imidazolate (Im⁻) groups was prepared to obtain a higher-temperature proton conductor than a Nafion membrane with water driving. The crystal is constructed by complementary N−H⋅⋅⋅N H-bonds between the Ru^III complexes and has a rare Icy-c* cubic network topology with a twofold interpenetration without crystal anisotropy. The crystals show a proton conductivity of 3.08×10⁻⁵ S cm⁻¹ at 450 K and a faster conductivity than those formed by only HIms. The high proton conductivity is attributed to not only molecular rotations and hopping motions of HIm frameworks that are activated at ∼113 K, but also isotropic whole-molecule rotation of [Ru^III(Him)₃(Im)₃] at temperatures greater than 420 K. The latter rotation was confirmed by solid-state ²H NMR spectroscopy; probable proton conduction routes were predicted and theoretically considered.     

Syntheses and properties of dumbbell‐shaped POSS derivatives linked by luminescent π‐conjugated units

Dumbbell‐shaped isobutyl‐substituted 1,2‐bis(4‐vinylphenyl)acetylene‐linked POSS (DA1), 9,10‐bis(4‐vinylphenyl)ethynyl)anthracene‐linked POSS (DA2), and 5,5″‐bis((4‐vinyl)phenyl)ethynyl)‐2,2′:5′2″‐terthiophene‐linked POSS (DA3), and corresponding model compounds were synthesized by cross metathesis and Sonogashira reaction, and their film formability, and thermal and optical properties were examined. The dumbbell structures of the obtained compounds were confirmed by ¹H‐, ¹³C‐, and ²⁹Si‐NMR and MALDI‐TOF‐MS analysis. The dumbbell‐shaped POSS compounds gave optically transparent films. All the model compounds, however, formed opaque films. All the films were emissive under UV irradiation. The dumbbell structures minimize longer wavelength shifts and improve emission efficiency of the luminescent π‐conjugated linker units in their solid states compared with the model compounds. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012.     

Synthesis of water-soluble C60-porphyrin hybrid compounds

Water-soluble C60-porphyrin hybrid molecules were first synthesized toward their pharmaceutical applications.     

Birefringence imaging of human skin by polarization-sensitive spectral interferometric optical coherence tomography

We have developed a spectral interferometric optical coherence tomography (OCT) system with polarization sensitivity that is able to measure a two-dimensional tomographic image by means of one-dimensional mechanical scanning. Our system, which has an axial resolution of 32 mum , calculates the distribution of each element of the Müller matrix of a measured object from 16 OCT images. The OCT system successfully reveals the birefringent nature of human skin tissue.     

Nuclear magnetic resonance spectra of carbanions—VI. Cumyl-, α-methylbenzyl- and benzyl carbanions

The proton magnetic resonance spectra of the three title carbanions have been observed in THF with potassium as a counter ion. The ortho-protons in the α-methylbenzyl carbanion are nonequivalent at room temperature. This shows that the α-carbon in this carbanion is in the near-sp² configuration. The aromatic proton chemical shifts of the benzylpotassium obtained here are at higher shielding than those of benzyllithium reported previously by Sandel and Freedman. This seems to arise from the different ionic nature of the bonds between carbon and metal in the carbanions.     

Observation of the Fano-Kondo antiresonance in a quantum wire with a side-coupled quantum dot

We have observed the Fano-Kondo antiresonance in a quantum wire with a side-coupled quantum dot. In a weak coupling regime, dips due to the Fano effect appeared. As the coupling strength increased, conductance in the regions between the dips decreased alternately. From the temperature dependence and the response to the magnetic field, we conclude that the conductance reduction is due to the Fano-Kondo antiresonance. At a Kondo valley with the Fano parameter q approximately 0, the phase shift is locked to pi/2 against the gate voltage when the system is close to the unitary limit in agreement with theoretical predictions by Gerland et al. [Phys. Rev. Lett. 84, 3710 (2000)].