Determination of inorganic phosphate by electroanalytical methods: A review

Determination of inorganic phosphate is of very high importance in environmental and health care applications. Hence knowledge of suitable analytical techniques available for phosphate sensing for different applications becomes essential. Electrochemical methods for determining inorganic phosphate have several advantages over other common techniques, including detection selectivity, stability and relative environmental insensitivity of electroactive labels. The different electrochemical sensing strategies adopted for the determination of phosphate using selective ionophores are discussed in this review. The various sensing strategies are classified based on the electrochemical detection techniques used viz., potentiometry, voltammetry, amperometry, unconventional electrochemical methods etc., The enzymatic sensing of phosphate coupled with electrochemical detection is also included. Various electroanalytical methods available in the literature are assessed for their merits in terms of selectivity, simplicity, miniaturisation, adaptability and suitability for field measurements.     

Synthesis of Some Novel Biologically Active Disperse Dyes Derived from 4-Methyl-2,6-dioxo-1-propyl-1,2,5,6-tetrahydro-pyridine-3-carbonitrile as Coupling Component and Their Colour Assessment on Polyester Fabrics

A series of novel azo-disperse dyes containing alkylhydrazonopyridinone structures were synthesized. 4-Methyl-2,6-dioxo-1-propyl-1,2,5,6-tetrahydropyridine-3-carbonitrile (8) is synthesized by one-pot synthesis using ethyl cyanoacetate, propylamine, and ethyl acetoacetate. Compound 8 is then coupled with aromatic and heteroaromatic diazonium salts to afford the corresponding aryl- and heteroaryl-4-methyl-2,6-dioxo-1-propyl-1,2,5,6-tetrahydropyridine-3-carbonitriles 12a,b and 13a-c. Structural assignments to the dyes were made using NMR spectroscopic methods. A high temperature dyeing method was employed to apply these dyes to polyester fabrics. Most of the dyed fabrics tested displayed very good light fastness levels and good wash fastness. Finally, the biological activity of the prepared dyes against Gram positive bacteria and Gram negative bacteria were evaluated.     

Finite-field evaluation of static (hyper)polarizabilities based on the linear-scaling divide-and-conquer method

This article describes the finite-field (FF) approach for calculating static (hyper)polarizabilities based on the divide-and-conquer (DC) method. The method is assessed by the Hartree?CFock (HF) and post-HF calculations of ??-conjugated model systems: a terminal donor or acceptor substituent on polyene chains. The DC?CFF approach enables the evaluation of molecular polarizabilities with highly accurate coupled-cluster theory. Numerical assessments demonstrate that the (hyper)polarizabilities calculated by the present DC?CFF method agree with the conventional FF results to within a few percent by employing an appropriate buffer size.     

Sleep disturbances in highly stress reactive mice: Modeling endophenotypes of major depression

Background  

Neuronal mechanisms underlying affective disorders such as major depression (MD) are still poorly understood. By selectively breeding mice for high (HR), intermediate (IR), or low (LR) reactivity of the hypothalamic-pituitary-adrenocortical (HPA) axis, we recently established a new genetic animal model of extremes in stress reactivity (SR). Studies characterizing this SR mouse model on the behavioral, endocrine, and neurobiological levels revealed several similarities with key endophenotypes observed in MD patients. HR mice were shown to have changes in rhythmicity and sleep measures such as rapid eye movement sleep (REMS) and non-REM sleep (NREMS) as well as in slow wave activity, indicative of reduced sleep efficacy and increased REMS. In the present study we were interested in how far a detailed spectral analysis of several electroencephalogram (EEG) parameters, including relevant frequency bands, could reveal further alterations of sleep architecture in this animal model. Eight adult males of each of the three breeding lines were equipped with epidural EEG and intramuscular electromyogram (EMG) electrodes. After recovery, EEG and EMG recordings were performed for two days.     

Highly sensitive optical sensor system for blood leakage detection

A highly sensitive method for the detection of blood leakage has been developed, and a practical sensor system for blood concentration measurement has been constructed. The present method is based on the attenuation of laser light by blood cells. The effects of the fluctuations of the incident laser light power are eliminated by normalizing the attenuated light intensity by the incident light intensity. A part of the incident laser light is reflected by a beam splitter mounted at the entrance of the test cell, of which the power is measured to provide base data for normalization. The optical path is extended to enhance sensitivity by using a pair of side mirrors. This multi-reflection method is very effective to increase sensitivity; the maximum sensitivity obtained for blood concentration is about 4 X 10^-6 by volume, which is significantly higher than that of the conventional sensors.     

On the Computations of Gas-Solid Mixture Two-Phase Flow

This paper presents high-resolution computations of a two-phase gas-solid mixture using a well-defined mathematical model. The HLL Riemann solver is applied to solve the Riemann problem for the model equations. This solution is then employed in the construction of upwind Godunov methods to solve the general initial-boundary value problem for the two-phase gas-solid mixture. Several representative test cases have been carried out and numerical solutions are provided in comparison with existing numerical results. To demonstrate the robustness, effectiveness and capability of these methods, the model results are compared with reference solutions. In addition to that, these results are compared with the results of other simulations carried out for the same set of test cases using other numerical methods available in the literature. The diverse comparisons demonstrate that both the model equations and the numerical methods are clear in mathematical and physical concepts for two-phase fluid flow problems.     

Dynamic hyperpolarizability calculations of large systems: the linear-scaling divide-and-conquer approach

We report a linear-scaling computation method for evaluating the dynamic first hyperpolarizability β based on the divide-and-conquer (DC) method. In the present scheme, we utilized the quasi-density-matrix expression derived from Wigner's (2n + 1) rule for β, where the quasi-density matrices are constructed from the solution obtained via the DC time-dependent self-consistent field (TD-SCF) method [T. Touma, M. Kobayashi, and H. Nakai, Chem. Phys. Lett. 485, 247 (2010)]. Numerical evaluation of π-conjugated and saturated organic chain systems verified that the present scheme considerably reduces the computational time for the β evaluation with a slight loss of accuracy, even around the singular frequency appearing at the electronic excitation energy. This evaluation indicates that the present linear-scaling TD-SCF scheme can also be used to estimate the molecular excitation energy. Furthermore, we succeeded in accurately evaluating the macroscopic second-harmonic generation coefficient of the polyvinylidene fluoride from the molecular (hyper)polarizabilities.     

Experimental and numerical analysis of two-phase infiltration in a partially saturated soil

The purpose of this study is to analyze the effects of the soil air flow on the process of water infiltration in a 93.5 cm deep vertical column for varied boundary conditions at the surface - positive time constant head; time constant fluxes smaller and greater than saturated soil hydraulic conductivity.Several experiments conducted on a sandy soil column with and without a possible air flow through the wall are presented. Continuous and simultaneous measurements of water content and air and water pressure heads at different depths allow the analysis of the air and water movements within the soil and the determination of the capillary pressure and relative permeability for each phase as functions of the volumetric water content.A numerical solution of the equations describing the simultaneous flow of air and water is compared with the experimental data and with the traditional one-phase flow modeling. The results show that the air movement may significantly affect water flow variables such as infiltration rates, water content profiles, and ponding times.Furthermore, some basic assumptions used in two-phase flow modeling, such as the hydrodynamic stability of the wetting fronts and the pertinence of the relative permeability concept, are discussed in the light of the experimental data.     

One- and two-photon-induced ring-cleavage reactions of strained benzocycloalkenes via hot molecules

The ring-cleavage reactions of a series of benzocycloalkenes were studied using an ArF excimer laser. Product formation was significantly suppressed in the presence of nitrogen; therefore, the presence of vibrationally excited states (hot molecules), as intermediates, was indicated. The product of highly strained benzocyclobutene was linearly proportional to the laser fluence, whereas those of benzocyclopentene and benzocyclohexene were proportional to the square of the laser fluence in the presence of nitrogen. These phenomena cannot be understood as photochemical bond cleavage in the electronic excited state, but instead appear to be the result of single- and two-photon reactions of hot molecules. The dissociation rate constants were evaluated by a statistical rate theory under the assumption that the reaction occurred from the hot molecule. The reaction rate of highly strained benzocyclobutene was predicted to be faster than the collisional rate with foreign gas, even if it had vibrational energy equivalent to one photon; however, the reaction rates of less strained benzocyclohexene were expected to compete with the collisional rate when the vibrational energy was equivalent to two photons. Benzocyclopentene was an intermediate case and showed both single- and two-photon reactions. The dissociation rate constant of 1.4 x 10(6) s(-1) was successfully obtained from benzocyclopentene under collision-free conditions. This value was in fair agreement with the calculated value. The different dissociation rate constants of the molecules were well-explained in terms of the strain energy. Although the strain energy varies in a wide range (10-130 kJ mol(-1)), the simple model of the calculations reproduced the observed values of the CH2-CH2 bond dissociation in strained benzocycloalkenes.