Simple and rapid determination of hydrogen peroxide using phosphine-based fluorescent reagents with sodium tungstate dihydrate.

A simple batch method for the fluorometric determination of hydrogen peroxide using phosphine-based fluorescent reagents has been developed. A rapid, mild and selective derivatization reaction was achieved by adding sodium tungstate dihydrate to the reaction mixture of hydrogen peroxide and a phosphine-based fluorescent reagent. When 4-diphenylphosphino-7-methylthio-2,1,3-benzoxadiazole was used as a reagent, the derivatization reaction was completed after 2 min at room temperature. The calibration curve was linear between 12.5 and 500 ng hydrogen peroxide in a 10 microL sample solution. This method is accurate and has potential for on-line applications.     

Dinuclear calcium complex with weakly NH...O hydrogen-bonded sulfonate ligands

The novel intramolecularly NH...O hydrogen-bonded Ca(II)-aryl sulfonate complex, [Ca2(SO3-2-t-BuCONHC6H4)2(H2O)4]n(2-t-BuCONHC6H4SO3)2n (1), sulfonate anion, (HNEt3)(SO3-2-t-BuCONHC6H4) (2a), (PPh4)(SO3-2-t-BuCONHC6H4) (2b), (n-Bu4N)(SO3-2-t-BuCONHC6H4) (2c), and sulfonic acid, 2-t-BuCONHC6H4SO3H (3), were synthesized. The structures of 1, 2a, and 2b depict the presence of the formation of NH...O hydrogen bonds between the amide NH and S-O oxygen for a series of compounds as determined by IR and 1H NMR analyses both in the solid state and in the solution state. Thus, the NH...O hydrogen bonds with neutral amide groups are available for investigation of the electronic state of the O- anion. The combined data from the IR and 1H NMR spectra indicate that the sulfonic acid, sulfonate anion, and Ca(II) complex have a substantially weak intramolecular NH...O hydrogen bond between the SO3 oxygen and amide NH. In the detailed comparison with the intense NH...O hydrogen bonds for the carboxylate, weak NH...O hydrogen bonds for sulfonate is due to the strong conjugation of the SO3- group with the lower nucleophilicity.     

Chitosan-Modified Carbon Nanotubes-Based Platform for Low-Density Lipoprotein Detection

We have fabricated an immunosensor based on carbon nanotubes and chitosan (CNT-CH) composite for detection of low density lipoprotein (LDL) molecules via electrochemical impedance technique. The CNT-CH composite deposited on indium tin oxide (ITO)-coated glass electrode has been used to covalently interact with anti-apolipoprotein B (antibody: AAB) via a co-entrapment method. The biofunctionalization of AAB on carboxylated CNT-CH surface has been confirmed by Fourier transform infrared spectroscopic and electron microscopic studies. The covalent functionalization of antibody on transducer surface reveals higher stability and reproducibility of the fabricated immunosensor. Electrochemical properties of the AAB/CNT-CH/ITO electrode have been investigated using cyclic voltammetric and impedimetric techniques. The impedimetric response of the AAB/CNT-CH/ITO immunoelectrode shows a high sensitivity of 0.953?Ω/(mg/dL)/cm² in a detection range of 0–120 mg/dL and low detection limit of 12.5 mg/dL with a regression coefficient of 0.996. The observed low value of association constant (0.34 M^–1s^–1) indicates high affinity of AAB/CNT-CH/ITO immunoelectrode towards LDL molecules. This fabricated immunosensor allows quantitative estimation of LDL concentration with distinguishable variation in the impedance signal.     

Structure of the monoclinic-form misfit-layer compound, (Ca0.85OH)2alpha CoO2 (alpha approximately 0.57822)

The incommensurate modulated crystal structure of the new misfit-layer calcium cobalt oxide (Ca0.85OH)2alphaCoO2 was investigated using a superspace-group formalism with synchrotron X-ray diffraction data. The compound is a kind of composite crystal that consists of two interpenetrating subsystems, [CoO2]infinity layers containing triangular lattices formed by edge-sharing CoO6 octahedra, separated from each other by [2Ca0.85OH]infinity double-layered rock-salt-type slabs. Both the subsystems are monoclinic lattices with the unit cell parameters, a1 = 2.8180(4) A, b = 4.8938(6) A, c = 8.810(1) A, alpha0 = 95.75(3) degrees , and alpha(=|q|=a1/a2) = 0.57822(8), viz., a2 = 4.8736 A, with Z = 2. A possible superspace group is C2/m(alpha10)s0-C21/m(alpha(-1)10) for the respective subsystems. The atomic positions deviate from the average positions of the fundamental structure due to the incommensurable periodic interaction between the subsystems. A significant structural modulation was found in the [2Ca0.85OH] subsystem, whereas the modulation in the [CoO2] subsystem is less than in [2Ca0.85OH], due to the tight bonding of the close-packed CoO6 octahedra. The degree of modulation in the CoO2 layers, i.e., the potential modulation, is almost the same as those of other compounds of the misfit-layer cobalt oxides. Flattened CoO6 octahedra indicate hole doping into the CoO2 layers. The [2Ca0.85OH] blocks act as the charge reservoir layers, and the defect Ca ions are presumably the source of the holes.     

ac ionic conductivity of hollandite type compounds from 100 Hz to 37.0 GHz

The frequency- and temperature-dependences of a.c. ionic conductivity of one-dimensional super-ionic conductors K-priderites with a hollandite type structures were investigated from 100 Hz to 37.0 GHz. Four kinds of K-priderite, K_1.6Mg_0.8Ti_7.2O₁₆, (K_1.3, Li_0.1) Mg_0.7Ti_7.3O₁₆, K_1.6Al_1.6Ti_6.4O₁₆ and (K_1.3, Li_0.2) Al_1.5Ti_6.5O₁₆, were studied. An equivalent circuit to combine the data of the complex conductivity at low and high frequencies was proposed. The data of complex conductivity at low frequencies can be analyzed in terms of the moving box model proposed by Beyeler et al. The transport of K⁺ ions at low frequencies is characterized by the cooperative motion of the K⁺ ions with various mobilities and is accompanied with the polarization of the K⁺ ions in the channels. The ion transport across intrinsic barriers at or above microwave frequencies is characterized by the frequency-independent ionic conductivity and is interpreted by the configurational model proposed by Beyeler et al. The height of intrinsic barriers is related to the lattice constants of a crystal.     

Topological nature of polarization and charge pumping in ferroelectrics

Electric polarization in insulators is represented by the transferred charge through a shift of the Bloch wave functions induced by an adiabatic change of external parameters Q-->. It is found that this covalent/quantum contribution is determined nonlocally by the topological structure in the Q--> space. The condition for the charge pumping for a cyclic change of Q--> is also obtained. Applications of this picture to various organic ferroelectrics and BaTiO3 are discussed.     

The effect of iron spin transition on electrical conductivity of (Mg,Fe)O magnesiowüstite

We measured the electrical conductivity of Mg_0.81Fe_0.19O magnesiowüstite, one of the important minerals comprising Earth’s lower mantle, at high pressures up to 135 GPa and 300 K in a diamond-anvil cell (DAC). The results demonstrate that the electrical conductivity increases with increasing pressure to about 60 GPa and exhibits anomalous behavior at higher pressures; it conversely decreases to around 80 GPa and again increases very mildly with pressure. These observed changes may be explained by the high-spin to low-spin transition of iron in magnesiowüstite that was previously reported to occur in a similar pressure range. A very small pressure effect on the electrical conductivity above 80 GPa suggests that a dominant conduction mechanism changes by this electronic spin transition. The electrical conductivity below 2000-km depth in the mantle may be much smaller than previously thought, since the spin transition takes place also in (Mg,Fe)SiO₃ perovskite.     

Oxygen isotope effect of superconducting (Nd1−xCex)2CuO4−δ system

The effect of oxygen isotope substitution on the transition temperature T_c of a superconducting (Nd_1−xCe_x)₂CuO_4−δ system was studied, where the special synthetic method was taken to minimize ambiguous factors on the oxygen concentration and to guarantee the complete substitution of ¹⁶O by ¹⁸O. The isotope exponent in the relationship of T_c∝1/M was estimated to be less than 0.15 by magnetic susceptibility measurements.