How accurate is the density functional theory combined with symmetry-adapted perturbation theory approach for CH-pi and pi-pi interactions? A comparison to supermolecular calculations for the acetylene-benzene dimer

Five different orientations of the acetylene-benzene dimer including the T-shaped global minimum structure are used to assess the accuracy of the density functional theory combined with symmetry adapted perturbation theory (DFT-SAPT) approach in its density-fitting implementation (DF-DFT-SAPT) for the study of CH-pi and pi-pi interactions. The results are compared with the outcome of counterpoise corrected supermolecular calculations employing second-order M?ller-Plesset (MP2), spin-component scaled MP2 (SCS-MP2) and single and double excitation coupled cluster theory including perturbative triple excitations (CCSD(T)). For all considered orientations MP2 predicts much deeper potential energy curves with considerably shifted minima compared to CCSD(T) and DFT-SAPT. In spite of being an improvement over the results of MP2, SCS-MP2 tends to underestimate the well depth while DFT-SAPT, employing an asymptotically corrected hybrid exchange-correlation potential in conjunction with the adiabatic local density approximation for the exchange-correlation kernel, is found to be in excellent agreement with CCSD(T). Furthermore, DFT-SAPT provides a detailed understanding of the importance of the electrostatic, induction and dispersion contributions to the total interaction energy and their repulsive exchange corrections.     

Cylindrospermopsin determination using 2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid (HEPES) as the internal standard

Cylindrospermopsin (CYN) was determined by liquid chromatography/electrospray ionization-mass spectrometry (LC/ESI-MS) using 2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid (HEPES) as the internal standard. In the selected ion monitoring of LC/ESI-MS, m/z 414 for CYN and 237 for HEPES were monitored using the negative mode; the retention times of CYN and HEPES were 12.41 and 14.21 min, respectively. CYN was determined from peak area ratios of m/z 414/237. By the treatment of an anion exchange cartridge using a buffer at pH 10.5, CYN was isolated and condensed. No interfering peak was observed. Linearity of this method was observed at the range of 0.10-31.12 ng. Total coefficients of variation were 5.1 and 2.9% at 104 and 1038 μg CYN L⁻¹. The quantitative limit at a signal-to-noise (S/N) ratio of 10 was 0.16 ng.CYN concentration in natural waters is low. CYN in waters should be condensed for determination. This method including the treatment for isolation and condensation of CYN is useful for determination of CYN in environmental and/or drinking waters.     

Spherical neutron polarimetry studies on the magnetic structure of single crystal Cr1−xMoxB2 (x=0, 0.15)

By applying spherical neutron polarimetry technique to Cr_1−xMo_xB₂ (x=0, 0.15), we successfully determined its precise magnetic structures. We emphasize here that the ratio of magnetic component was determined by measuring the two satellite reflections and rotating the incident neutron spin directions.     

Experimental determination of interfacial energies for Ag2Al solid solution in the CuAl2--Ag2Al system

The equilibrated grain boundary groove shapes of solid solution Ag2Al in equilibrium with an Al-Cu-Ag liquid were observed from a quenched sample with a radial heat flow apparatus.The Gibbs-Thomson coefficient,solid-liquid interfacial energy and grain boundary energy of the solid solution Ag2Al have been determined from the observed grain boundary groove shapes.The thermal conductivity of the solid phase and the thermal conductivity ratio of the liquid phase to solid phase for Ag2Al-28.3 at the %CuAl2 alloy at the melting temperature have also been measured with a radial heat flow apparatus and Bridgman type growth apparatus,separately.     

Hamiltonian map approach to 1D Anderson model

A one-dimensional diagonal tight binding electronic system is analyzed with the Hamiltonian map approach to study analytically the inverse localization length of an infinite sample. Both the uncorrelated and the dichotomic correlated random potential sequences are considered in the evaluations of the inverse localization length. Analytical expressions for the invariant measure or the angle density distribution are the main motivation of this work in order to derive analytical results. The well-known uncorrelated weak disorder result of the inverse localization length is derived with a clear procedure. In addition, an analytical expression for high disorder is obtained near the band edge. It is found that the inverse localization length goes to 1 in this limit. Following the procedure used in the uncorrelated situation, an analytical expression for the inverse localization length is also obtained for the dichotomic correlated sequence in the small disorder situation.     

A simple flow injection spectrophotometric determination method for iron(III) based on O-acetylsalicylhydroxamic acid complexation

A simple and rapid flow-injection spectrophotometric method for the determination of iron(III) and total iron is proposed. The method is based on the reaction between iron(III) and O-acetylsalicylhydroxamic acid (AcSHA) in a 2 % methanol solution resulting in an intense violet complex with strong absorption at 475 nm. Optimum conditions for the determination of iron(III) and the interfering ions were tested. The relative standard deviation for the determination of 5 μg L⁻¹ iron(III) was 0.85 % (n = 10), and the limit of detection (blank signal plus three times the standard deviation of the blank) was 0.5 μg L⁻¹, both based on the injection volumes of 20 μL. The method was successfully applied in the determination of iron(III) and total iron in water and ore samples. The method was verified by analysing a certified reference material Zn/Al/Cu 43XZ3F and also by the AAS method.     

Properties of a Non-Aromatic Epoxy Polymer-Based Monolithic Capillary Column for μ-HPLC

We report the chromatographic properties of a new type of epoxy polymer-based monolithic capillary column, the Tetrad-C column. The column was prepared by a completely new method—reaction of a tetra-functional epoxy monomer, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (trade name Tetrad-C), with a diamine, 4-[(4-aminocyclohexyl)methyl)cyclohexane (BACM). This polymer monolith has no aromatic functional groups reducing chromatographic performance. The columns were carefully observed by scanning electron microscopy and evaluated chromatographically by use of a μ-HPLC system. It was found that morphological control of the epoxy polymer-based monolith was possible simply by changing the polymerization conditions, i.e., the polymerization temperature and/or the relative amounts of porogenic solvent and BACM. Another advantage was that volumetric shrinkage of the tetra-functional epoxy-based monolith during the polymerization reaction was much less than for the tri-functional epoxy-based monolithic (TEPIC) column reported in our previous paper. A Tetrad-C column 200 mm long afforded up to 10,000 plates for alkylbenzenes in reversed-phase-mode. This column can also work in HILIC mode, although the hydrophobicity of the column was greater than that of the TEPIC column. Heat treatment (160 °C for 2 h; to eliminate residual, unreacted, functional groups) had a negligible effect on column performance, indicating the columns were thermally stable.     

Quantitative analysis of ezetimibe in human plasma by gas chromatography‐mass spectrometry

A new, specific and sensitive GC‐MS method with electron impact ionization technique was developed for quantitative analysis of ezetimibe (EZE) in human plasma. Prior to GC analysis, EZE was derivatized with N‐methyl‐N‐trimethylsilyl‐trifluoroacetamide (MSTFA), which is a trimethyl silylating reagent. The derivatization reaction was optimized and parameters such as catalyst, derivatization time, temperature, solvent and the volume of silylating reagent were investigated. Trimethylsilyl ether derivative of EZE was determined in selected ion monitoring (SIM, mass‐to‐charge ratio (m/z): 326) mode. The method was validated with respect to LOD and LOQ, precision, accuracy, linearity, specificity, stability, and recovery. The LOQ and LOD were found as 15 and 10 ng/mL, respectively. The linearity of the method ranged from 15 to 250 ng/mL. The correlation coefficient of the calibration curve was 0.9977 ± 0.0004 (± S.E.M.). The intra‐ and inter‐day precisions (RSD) were less than 6% and accuracies (bias) for intra‐ and inter‐day accuracy were found between –4.04 and 9.71% at four different concentration levels (15, 40, 100, 250 ng/mL). The proposed method was successfully applied to real human plasma samples for determination of total EZE.     

MHD mixed convection of a viscous dissipating fluid about a permeable vertical flat plate

The problem of steady laminar magnetohydrodynamic (MHD) mixed convection heat transfer about a vertical plate is studied numerically, taking into account the effects of Ohmic heating and viscous dissipation. A uniform magnetic field is applied perpendicular to the plate. The resulting governing equations are transformed into the non-similar boundary layer equations and solved using the Keller box method. Both the aiding-buoyancy mode and the opposing-buoyancy mode of the mixed convection are examined. The velocity and temperature profiles as well as the local skin friction and local heat transfer parameters are determined for different values of the governing parameters, mainly the magnetic parameter, the Richardson number, the Eckert number and the suction/injection parameter, f_w. For some specific values of the governing parameters, the results agree very well with those available in the literature. Generally, it is determined that the local skin friction coefficient and the local heat transfer coefficient increase owing to suction of fluid, increasing the Richardson number, Ri (i.e. the mixed convection parameter) or decreasing the Eckert number. This trend reverses for blowing of fluid and decreasing the Richardson number or decreasing the Eckert number. It is disclosed that the value of Ri determines the effect of the magnetic parameter on the momentum and heat transfer.