Investigation of drift gas selectivity in high resolution ion mobility spectrometry with mass spectrometry detection

Recent studies in electrospray ionization (ESI)/ion mobility spectrometry (IMS) have focussed on employing different drift gases to alter separation efficiency for some molecules. This study investigates four structurally similar classes of molecules (cocaine and metabolites, amphetamines, benzodiazepines, and small peptides) to determine the effect of structure on relative mobility changes in four drift gases (helium, nitrogen, argon, carbon dioxide). Collision cross sections were plotted against drift gas polarizability and a linear relationship was found for the nineteen compounds evaluated in the study. Based on the reduced mobility database, all nineteen compounds could be separated in one of the four drift gases, however, the drift gas that provided optimal separation was specific for the two compounds.     

Spatial distribution and risk assessment of radioactivity and heavy metal levels of sediment,surface water and fish samples from Lake Van,Turkey

In this study, radioactivity levels of 228 lake water samples, 63 upper and depth sediment samples and 12 fish samples from Lake Van were investigated from 2005 to 2008 and the distribution patterns of the radionuclides were presented. Analysis included gross alpha–beta and total radium isotopes activities and uranium concentrations of the water, and gross alpha and gross beta activities and relevant ²³⁸U, ²³²Th and ⁴⁰K activity of the sediment and fish samples of the lake. Mean gross alpha, gross beta and radium isotopes activities of lake water were found 0.74 ± 0.46, 0.02 ± 0.01 and 0.06 ± 0.04 Bq/L, respectively. Mean gross alpha and beta activities in upper and depth sediments were found to be 41 ± 6 and 1,514 ± 74 Bq/kg; 77 ± 5 and 394 ± 24 Bq/kg at a 95 % confidence level, respectively. Mean activities of ²³⁸U, ²³²Th and ⁴⁰K activity concentrations in upper and depth sediments were determined to be 225 ± 22, 70 ± 7 and 486 ± 39 Bq/kg; 174 ± 4, 63 ± 3 and 263 ± 25 Bq/kg, respectively. The mean gross alpha and beta, ²³⁸U, ²³²Th and ⁴⁰K aktivities in fish samples were established as 47 ± 18, 470 ± 12, 0.57 ± 0.220, 0.022 ± 0.006, 319 ± 11 Bq/kg, respectively. The transfer factor from lake water to fish tissues, annual intake by humans consuming fish, and annual committed effective doses were estimated and evaluated.     

A periodic DFT study of water and ammonia adsorption on anatase TiO2 (001) slab

Water and ammonia adsorption mechanisms on anatase TiO₂ (001) slab surface are investigated by means of periodic DFT approach. Molecular and dissociative adsorption energies for water are calculated to be ? 15 kcal/mol and ? 32 kcal/mol, respectively. Similarly, molecular and dissociative adsorption energies of ammonia on the same surface are found as ? 25 kcal/mol and ? 20 kcal/mol. A reverse result in this order is reached for the previous case of ONIOM cluster study (? 23 kcal/mol and ? 37 kcal/mol, respectively). The vibration frequency values are computed for the optimized geometries of adsorbed water and ammonia molecules on anatase TiO₂ (001) slab surface and compared with the values reported in the literature.     

Complexity Classes and Completeness in Algebraic Geometry

Foundations of Computational Mathematics - We study the computational complexity of sequences of projective varieties. We define analogues of the complexity classes P and NP for these and prove the...     

A rational approximate solution for generalized pantograph‐delay differential equations

In this paper, a new rational approximation based on a rational interpolation and collocation method is proposed for the solutions of generalized pantograph equations. A comprehensive error analysis is provided. The first part of the error analysis gives an upper bound for the absolute error. The second part is based on residual error procedure that estimates the absolute error. Some numerical examples are given to illustrate the method. The theoretical results support the numerical results. Copyright © 2015 John Wiley & Sons, Ltd.     

Temperature-dependent optical properties of GaSe layered single crystals

Optical properties of GaSe single crystals have been investigated using temperature-dependent transmission and room temperature reflection measurements in the wavelength range of 380–1100 nm. The analysis of the absorption data at room temperature showed the existence of indirect transitions in the crystal with energy band gap of 1.98 eV. Temperature dependence of the transmission measurements revealed the shift of the absorption edge toward lower energy as temperature is increased from 10 to 280 K. The rate of change of the indirect band gap was found as γ = ?6.6 × 10^?4 eV/K from the analysis of experimental data under the light of theoretical relation giving the band gap energy as a function of temperature. The absolute zero value of the band gap energy and Debye temperature were calculated from the same analysis. The Wemple–DiDomenico single-effective-oscillator model applied to refractive index dispersion data was used to determine the oscillator energy, dispersion energy, oscillator strength and zero-frequency refractive index values.     

Simultaneous detection of L-glutamate and nitric oxide from adherently growing cells at known distance using disk shaped dual electrodes

An ex vivo system for simultaneous detection of nitric oxide (NO) and L-glutamate using integrated dual 250 microm platinum disk electrodes modified individually with suitable sensing chemistries has been developed. One of the sensors was coated with an electrocatalytic layer of Ni tetrasulfonate phthalocyanine tetrasodium salt (Ni-TSPc) covered by second layer of Nafion, which stabilises on the one hand the primary oxidation product NO(+) and prevents interferences from negatively charged compounds such as NO(2)(-). For glutamate determination, the second electrode was modified with a crosslinked redox hydrogel consisting of Os complex modified poly(vinylimidazol), glutamate oxidase and peroxidase. A manual x-y-z micromanipulator on top of an inverted optical microscope was used to position the dual electrode sensor at a defined distance of 5 microm from a cell population under visual control. C6 glioma cells were stimulated simultaneously with bradykinin or VEGF to release NO while KCl was used to invoke glutamate release. For evaluation of the glutamate sensors, in some experiments HN10 cells were used. To investigate the sensitivity and reliability of the system, several drugs were applied to the cells, e.g. Ca(2+)-channel inhibitors for testing Ca(2+)-dependence of the release of NO and glutamate, rotenone for inducing oxidative stress and glutamate antagonists for analysing glutamate release. With these drugs the NO and glutamate release was modulated in a similar way then expected from previously described systems or even in-vivo measurements. We therefore conclude that our system is suitable to analyse stress-induced mechanisms in cell lines.     

Modelling of the blanking process of high-carbon steel using Lemaitre damage model

This paper presents a methodology to model a blanking process using a continuum mechanical damage model. A variant of the Lemaitre model, in which the quasi-unilateral conditions are taken into consideration to modify the damage behavior under compressive stress states, is selected as material model. S45C high-carbon steel is analyzed experimentally. To characterize the damage behavior of the material, notched round bar tensile tests with three different notch radii (6 mm, 10 mm, and 20 mm) using image analysis are performed. Using digital image processing, the strain at the deformation zone can be computed for the load–strain curves. Those curves are used as an objective function to determine the parameters of the Lemaitre damage model. The experimental results are compared with the results of the FE analysis of the tensile test. The identified model parameters are used in numerical investigations of axisymmetric blanking. The effect of the model's extension to quasi-unilateral damage evolution is discussed. The crack progress in high-carbon steel sheet during blanking and the final sheared part morphology are predicted and compared with the experimental results. Sheared surface and burr height obtained by the analysis coincide with the results of the blanking experiment.     

Electrospray ionization ion mobility spectrometry of carboxylate anions: ion mobilities and a mass-mobility correlation

A number of carboxylate anions spanning a mass range of 87-253 amu (pyruvate, oxalate, malonate, maleate, succinate, malate, tartarate, glutarate, adipate, phthalate, citrate, gluconate, 1,2,4-benzenetricarboxylate, and 1,2,4,5-benzenetetracarboxylate) were investigated using electrospray ionization ion mobility spectrometry. Measured ion mobilities demonstrated a high correlation between mass and mobility in both N2 and CO2 drift gases. Such a strong mass-mobility correlation among structurally dissimilar ions suggests that the carboxylate functional group that these ions have in common is the source of the correlation. Computational analysis was performed to determine the most stable conformation of the studied carboxylate anions in the gas phase under the current experimental conditions. This analysis indicated that the most stable conformations for multicarboxylate anions included intramolecular hydrogen-bonded ring structures formed between the carboxylate group and the neutral carboxyl group. The carboxylate anions that form ring confirmations generally show higher ion mobility values than those that form extended conformations. This is the first observation of intramolecular hydrogen-bonded ring conformation of carboxylate anions in the gas phase at atmospheric pressure.