Extraction—spectrophotometric determination of cadmium with diphenylcarbazone in the presence of 1,10-phenanthroline

The addition of 1,10-phenanthroline improves both the extraction and the spectrophotometric sensitivity of the determination of cadmium with diphenylcarbazone. Slope analysis suggests the formation of a 1:2:2 extracted species. The molar absorptivity is 9.4 × 10⁴ l cm^-1 mol^-1 at 536 nm and extraction is maximal at pH 8.2–9.8. Extraction is rapid and absorbances remain constant at room temperature for 48 h. Various divalent metal ions interfere.     

Low-temperature heat capacity of room-temperature ionic liquid, 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Heat capacities of liquid, stable crystal, and liquid-quenched glass of a room-temperature ionic liquid (RTIL), 1-hexyl-3-methylimidazolium bis(trifluromethylsulfonyl)imide were measured between 5 and 310 K by adiabatic calorimetry. Heat capacity of the liquid at 298.15 K was determined for an IUPAC project as (631.6 +/- 0.5) J K(-1) mol(-1). Fusion was observed at T(fus) = 272.10 K for the stable crystalline phase, with enthalpy and entropy of fusion of 28.34 kJ mol(-1) and 104.2 J K(-1) mol(-1), respectively. The purity of the sample was estimated as 99.83 mol % by the fractional melting method. The liquid could be supercooled easily and the glass transition was observed around T(g) approximately 183 K, which was in agreement with the empirical relation, T(g) approximately ((2)/(3)) T(fus). The heat capacity of the liquid-quenched glass was larger than that of the crystal as a whole. In the lowest temperature region, however, the difference between the two showed a maximum around 6 K and a minimum around 15 K, at which the heat capacity of the glass was a little smaller than that of crystal.     

Phase transformations in bulk nanostructured potassium niobiosilicate glasses

In potassium niobiosilicate (KNS) glasses, nanostructuring can be driven and controlled by thermal treatments at the glass transition temperature and/or by modulation of the chemical composition. The tight relationship between nanostructure and nonlinear optical properties suggests these bulk nanomaterials as an appealing route to nanophotonics. The focus of this paper is placed on assessing the phase transformations which occur in these materials upon annealing at the glass transition temperature and subsequent heating. High-temperature resolved X-ray diffraction (HTXRD) and high-resolution transmission electron microscopy (HRTEM) experiments are integrated with previously published results for in-depth insight. It will be shown that nanostructuring evolves from nucleation of niobium-rich nanocrystals, which are up to 20 nm large, uniformly distributed in the matrix bulk, and metastable. Formation kinetics as well as phase transformation of the nanocrystals are determined by the glass composition. Depending on it, nanocrystal nucleation can be preceded or not by phase separation, and the nanocrystals' phase transition can be of first or second order.     

Synthesis of a phosphorus-containing hybrid porphyrin

A phosphorus-containing hybrid porphyrin was successfully prepared via the BF3-promoted dehydrative condensation between sigma4-phosphatripyrrane and 2,5-bis[hydroxy(phenyl)methyl]thiophene. The NMR and UV-vis absorption spectra, electrochemical measurements, and DFT calculations revealed that the sigma3-P,N2,S-hybrid porphyrin exhibits high aromaticity as an 18pi-electron system in terms of both geometric and magnetic criteria. [structure: see text]     

Fast enclosure for all eigenvalues in generalized eigenvalue problems

A fast method for enclosing all eigenvalues in generalized eigenvalue problems Ax=λBx is proposed. Firstly a theorem for enclosing all eigenvalues, which is applicable even if A is not Hermitian and/or B is not Hermitian positive definite, is presented. Next a theorem for accelerating the enclosure is presented. The proposed method is established based on these theorems. Numerical examples show the performance and property of the proposed method. As an application of the proposed method, an efficient method for enclosing all eigenvalues in polynomial eigenvalue problems is also sketched.     

pH-responsive movement of cucurbit[7]uril in a diblock polypseudorotaxane containing dimethyl beta-cyclodextrin and cucurbit[7]uril

[Structure: see text] A polypseudorotaxane consisting of cucurbit[7]uril (CB[7])/N,N'-(3-phenylenebis(methylene)dipropargylamine (PMPA), [2]pseudorotaxane, and 2,6-O-dimethyl beta-cyclodextrin (DM-beta-CD)/alpha,omega-bisazidopropylene glycol 400 [2]pseudorotaxane was synthesized using the "click" reaction. The polypseudorotaxane structure was maintained in aqueous solution over a wide range of pH values with the DM-beta-CD units contributing to increased solubilization of the polypseudorotaxane without dethreading. The pH-responsive movement of the CB[7] units in the polypseudorotaxane was also observed.     

Thermal Conductivity of poly-p-phenylene-2,6-benzobisoxazole Film along the In-Plane Axis in the 10–300 K Temperature Range

The thermal conductivities of compression molded thin films of poly-p-phenylene-2,6-benzobisoxazole (PBO) were measured in directions along an in-plane axis in the 10–300?K temperature range by a steady-state heat flow method, with interest in the use of the material for superconductivity applications. The thermal conductivities of the PBO films increased from 0.3?W/mK to 9.0?W/mK with increasing temperature from 10?K to 300?K and these were much higher than those of polyimide films, epoxy resin and glass fiber reinforced plastics at all temperatures. The 9.0?W/mK at 300?K was 60% of that of stainless steel (SUS304). It was 6?W/mK at 150?K, which was half that of SUS304 and was 3.3?W/mK at 77?K, which was 33% of that of SUS304. The thermal conductivities of the PBO films were lower than those of a cloth of high strength ultrahigh molecular weight polyethylene fiber reinforced plastics in the 30?K–180?K temperature range and were almost equivalent to its values in the 180?K–300?K temperature range. The main contribution to the thermal conduction in the PBO films was from thermal phonon conduction along the molecular chains. Although many kinds of high thermal conductivity polymeric materials have been prepared by a uni-directional drawing process or by adding high thermal conductive additives, the PBO film showed high thermal conductivity without a uni-directional drawing process or high thermal conductive additive.     

常温下从离子液体电解液中电沉积金属钴

研究了离子液体镀液中Co、Zn的共沉积行为。ZnCl2-EMIC -CoCl2电解液的循环伏安曲线上出现了三个电流峰,对应的电极电位分别为250mV、50mV、-200mV（vs. Zn2+/Zn）。结合EDS成分分析,可断定这三个电流峰分别对应着Co的电沉积、Co电极上Zn的欠电位沉积和Co-Zn合金的电沉积。恒电位沉积表明,当控制阴极电位在100 mV（vs. Zn2+/Zn）左右时,可得到高纯度的钴镀层;若进行恒电流沉积,则当电流密度为85mA/cm2左右时能够得到高纯度的钴镀层。对Co、Zn的共沉积机理研究表明,Co的电沉积过程和Zn 在Co上的欠电位沉积过程均受扩散过程控制。     

Stern-gerlach study of multidecker lanthanide-cyclooctatetraene sandwich clusters

Multilayer lanthanide-cyclooctatetraene organometallic clusters, Lnn(C8H8)m (Ln = Eu, Tb, Ho, Tm; n = 1-7; m = n - 1, n, n + 1) were produced by a laser vaporization synthesis method. The magnetic deflections of these organometallic sandwich clusters were measured by a molecular beam magnetic deflection technique. Most of the sandwich species displayed one-sided deflection, while some of smaller Ln-C8H8 clusters showed symmetric broadening without or with only very small (or absent) net high-field deflection. In general, the total magnetic moments, calculated from the magnitude of the beams deflections, increase with the number of lanthanide atoms (i.e., with increasing sandwich layers); however for Tb-, Ho-, and Tm-C8H8 clusters with n > 3, the suppression of the magnetic moments was observed, possibly through antiferromagnetic interactions. For Eu-C8H8 clusters, we observe a linear increase of the magnetic moments with the number of Eu atoms up to n = 7, with average magnetic moment per Eu atom around 7 muB--similar to that displayed by conventionally synthesized mononuclear EuIIC8H8 complexes, indicating that Eu atoms exist as Eu2+ ions in the full sandwich Eun(C8H8)n+1 clusters. These results suggest that Eun(C8H8)n+1 is a promising candidate for a high-spin, one-dimensional building block in organometallic magnetic materials.     

Comparative study on the structural, optical, and electrochemical properties of bithiophene-fused benzo[c]phospholes

Three types of bithiophene-fused benzo[c]phospholes were successfully prepared by Ti(II)-mediated cyclization of the corresponding dialkynylated bithiophene derivatives as a key step. Each sigma(3)-phosphorus center of the benzo[c]phosphole subunits was readily transformed into sigma(4)-phosphorus center by Au coordination or oxygenation. In addition, the bithiophene subunit was functionalized at the alpha,alpha'-carbon atoms by Pd-catalyzed cross-coupling reactions with heteroarylmetals and by an S(N)Ar reaction with hexafluorobenzene. The experimentally observed results (NMR spectroscopy, X-ray analysis, UV/Vis absorption/fluorescence spectroscopy, and cyclic/differential-pulse voltammetry) have revealed that the structural, optical, and electrochemical properties of the bithiophene-fused benzo[c]phospholes vary considerably depending on the pi-conjugation modes at the bithiophene subunits and the substituents of the heterocyclopentadiene components. The appropriately ring-annulated sigma(3)-P derivatives and sigma(4)-P-AuCl complexes were found to emit fluorescence in the orange-red region, and the sigma(4)-P-oxo derivatives proved to undergo reversible one-electron reduction at -1.4 to -1.8 V (vs ferrocene/ferrocenium). These results indicate that the bithiophene-fused benzo[c]phospholes possess narrow HOMO-LUMO gaps and low-lying LUMOs, which was confirmed by density functional theory calculations of their model compounds. The time-of-flight measurement of an ITO/benzo[c]phosphole/Al device showed that the electron mobility in the P-oxo derivative is one-order higher than that in Alq(3) at low electric fields. The present study demonstrates that the arene-fused benzo[c]phosphole skeleton could be a highly promising platform for the construction of a new class of phosphole-based optoelectrochemical materials.