Quantum chemical calculation of exchange interactions in supramolecularly arranged N,N′‐dioxy‐2,6‐diazaadamantane organic biradical

Quantum mechanical exchange effects in purely organic N,N′‐dioxy‐2,6‐diazaadamantane biradical derivatives with promesogenic substituents have been studied. To determine intermolecular exchange energies, packing conditions of the radical core units in layered liquid crystalline phases are simulated using the Gaussian 09 program. The broken symmetry approach gives J ≈ 7 cm^?1 for intramolecular ferromagnetic exchange interactions between nitroxyl radical centers in one molecule. Both ferromagnetic and antiferromagnetic intermolecular interactions are possible in this kind of systems according to the obtained calculation results. Depending on the mutual positioning and orientation of molecules, the intermolecular antiferromagnetic exchange constant can reach a value of ?50 cm^?1, and the intermolecular ferromagnetic constant a value of 10 cm^?1. The simultaneous presence of intramolecular and intermolecular exchange between spin‐carrying centers in this kind of supramolecularly ordered multispin systems is favorable for the formation of magnetically interacting chains and two‐dimensional networks. © 2016 Wiley Periodicals, Inc.     

In-situ sorbent formation for the extraction of pesticides from honey

An organic polymer was re-precipitated in solution to use as an adsorbent in dispersive solid-phase extraction of some pesticides from honey samples prior to their determination by high-performance liquid chromatography-tandem mass spectrometry. In this approach, different deep eutectic solvents were prepared using lysine and their ability in elution of the analytes from the adsorbent surface was tested. A diluted honey solution was transferred into a glass test tube and then a solution of polystyrene dissolved in dimethylformamide was injected into the solution. By doing this, polystyrene is re-precipitated in the solution and dispersed in whole parts of it as many tiny particles. Then the mixture was centrifuged and the adsorbed analytes on the particles were eluted using a proper hydrophilic deep eutectic solvent. The central composite design approach was used for the optimization of effective parameters. The limits of detection and quantification were in the ranges of 0.06–0.20 and 0.22–0.69 ng/g, respectively. The calibration curves obtained by matrix-matched standard solutions were linear in the range of 0.69–500 ng/g with a coefficient of determinations ≥0.9962. The method provided high extraction recoveries (70–99%) and enrichment factors (140–198), and an acceptable precision (relative standard deviations ≤7.1%).     

Polymer Chain Dynamics Predicted by n-Renormalized Rouse Models: Numerical Studies

Features of the renormalized and twice renormalized Rouse models were examined numerically. Based on numerical evaluations of the generalized Langevin equation in renormalization approaches, nonexponential normal mode autocorrelation functions were derived, that can be described over two orders of magnitude by stretched exponential functions. The mode number dependence of the stretching parameter was evaluated. The consequences of the nonexponential correlation functions on dynamical properties are discussed. As a basis for predictions for the behavior of diffusion and spin-lattice relaxation dispersion, the time dependence of the mean-squared segment displacement and of the autocorrelation function of the segment tangential vector, respectively, were obtained taking into account finite chain lengths.     

Reactions of dithioxo‐1,3,2λ5,4λ5‐dithiadiphosphetanes with antimony(III) alkoxides

New antimony(III) derivatives of dithiophosphonic and trithiophosphoric acids 3a–c and 5 were obtained by the reactions of Lawesson's reagent 1a, its homologue 1b, and the isobutyl homologue of Davy's reagent 4 with antimony(III) alkoxides 2a–c. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 399–403, 1999     

Conformational analyses of bacillomycin D, a natural antimicrobial lipopeptide, alone or in interaction with lipid monolayers at the air-water interface

Bacillomycin D is a natural antimicrobial lipopeptide belonging to the iturin family. It is produced by Bacillus subtilis strains. Bacillomycin D is characterized by its strong antifungal and hemolytic properties, due to its interaction with the plasma membrane of sensitive cells. Until now, only few limited analyses were conducted to understand the biological activities of bacillomycin D at the molecular level. Our purpose was to analyze the conformation of bacillomycin D using IR spectroscopy and to model its interactions with cytoplasmic membranes using Langmuir interfacial monolayers. Our findings indicate that bacillomycin D contains turns and allow to model its three-dimensional structure. Bacillomycin D formed a monolayer film at the air-water interface and kept its turn conformation, as shown by polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS). To identify the membrane lipid target of bacillomycin D, its interactions with pure lipid monolayers were analyzed and an original behavior of the lipopeptide toward cholesterol-containing monolayers was shown. This original behavior was lost when bacillomycin D was interacting with pure cholesteryl acetate monolayers, suggesting the involvement of the alcohol group of cholesterol in the lipopeptide-cholesterol interaction.     

A novel polythiophene – ionic liquid modified clay composite solid phase microextraction fiber: Preparation,characterization and application to pesticide analysis

This report comprises the novel usage of polythiophene – ionic liquid modified clay surfaces for solid phase microextraction (SPME) fiber production to improve the analysis of pesticides in fruit juice samples. Montmorillonite (Mmt) clay intercalated with ionic liquids (IL) was co-deposited with polythiophene (PTh) polymer coated electrochemically on an SPME fiber. The surface of the fibers were characterized by using scanning electron microscopy (SEM). Operational parameters effecting the extraction efficiency namely; the sample volume and pH, adsorption temperature and time, desorption temperature and time, stirring rate and salt amount were optimized. In order to reveal the major effects, these eight factors were selected and Plackett–Burman Design was constructed. The significant parameters detected; adsorption and temperature along with the stirring rate, were further investigated by Box–Behnken design. Under optimized conditions, calibration graphs were plotted and detection limits were calculated in the range of 0.002–0.667 ng mL⁻¹. Relative standard deviations were no higher than 18%. Overall results have indicated that this novel PTh-IL-Mmt SPME surface developed by the aid of electrochemical deposition could offer a selective and sensitive head space analysis for the selected pesticide residues.     

Extraction,preconcentration and spectrophotometric determination of trace levels of thiosulfate in environmental waters

In the existing study, a new vortex-assisted cloud point extraction (VA-CPE) method was developed for determination of low levels of thiosulfate in environmental waters at 632 nm by spectrophotometry. The method is selectively based on charge-transfer-sensitive ion-pair complex formation of Ag(S₂O₃)₂ ^3?, which is produced by the reaction of thiosulfate with excess Ag⁺ ions with toluidine blue (3-amino-7-dimethylamino-2-methylphenazathionium chloride, TB⁺) and then its extraction into micellar phase of polyethylene glycol 4-tert-octylphenyl ether (Triton X-45) in presence of Na₂SO₄ as salting-out agent at pH 7.0. All the factors affecting complex formation and VA-CPE efficiency were optimized in detail. Under the optimized conditions, the linear calibration curves for thiosulfate were in the range of 0.2–120 and 5–180 µg L^?1 with sensitivity improvement of 81-folds and 15-folds, respectively, as a result of efficient mass transfer obtained by CPE with and without vortex, while it changed in the range of 260–3600 µg L^?1 without preconcentration at 642 nm. The limits of detection and quantification of the method for VA-CPE were found to be 0.05 and 0.22 µg L^?1, respectively. The precision (expressed as the percent relative standard deviation) was in range of 2.5–4.8% (5, 10 and 25 µg L^?1, n: 5). The method accuracy was validated by comparing the results to those of an independent 5,5′-dithiobis(2-aminobenzoic acid) (DTNB) method as well as recovery studies from spiked samples. It has been observed that the results are statistically in a good agreement with those obtained by DTNB method. Finally, the method developed was successfully applied to the preconcentration and determination of trace thiosulfate from environmental waters.     

Dynamics and interaction of pulses in the modified Manakov model

The two-component vector nonlinear Schrödinger equation, with mixed signs of the nonlinear coefficients, is considered. This equation is integrable by the inverse scattering transform method. The evolution of a single pulse and interaction of pulses are studied. It is shown that the dynamics of a single pulse is reduced to the scalar nonlinear Schrödinger equation of focusing or defocusing type, depending on the initial parameters. It is found that the interaction of pulses results in the appearance of additional solitons and bound states of several solitons. The asymptotic field profile in the non-soliton regime is also obtained.     

A numerically efficient method for the MAP/D/1/K queue via rational approximations

The Markovian Arrival Process (MAP), which contains the Markov Modulated Poisson Process (MMPP) and the Phase-Type (PH) renewal processes as special cases, is a convenient traffic model for use in the performance analysis of Asynchronous Transfer Mode (ATM) networks. In ATM networks, packets are of fixed length and the buffering memory in switching nodes is limited to a finite numberK of cells. These motivate us to study the MAP/D/1/K queue. We present an algorithm to compute the stationary virtual waiting time distribution for the MAP/D/1/K queue via rational approximations for the deterministic service time distribution in transform domain. These approximations include the well-known Erlang distributions and the Padé approximations that we propose. Using these approximations, the solution for the queueing system is shown to reduce to the solution of a linear differential equation with suitable boundary conditions. The proposed algorithm has a computational complexity independent of the queue storage capacityK. We show through numerical examples that, the idea of using Padé approximations for the MAP/D/1/K queue can yield very high accuracy with tractable computational load even in the case of large queue capacities.This work was done when the author was with the Bilkent University, Ankara, Turkey and the research was supported by TÜBITAK under Grant No. EEEAG-93.