Correlation of substituted aromatic β‐diketones' characteristic protons chemical shifts with Hammett substituent constants

Influence of dibenzoylmethane's substituents in meta and para positions on chemical shift values of tautomers' characteristic protons was investigated in four solvents with ¹H NMR spectroscopy: acetone‐d₆, benzene‐d₆, CDCl₃ and deuterated dimethyl sulfoxide (DMSO‐d₆). It was proved that the influence of substituents on chemical shifts strongly depends on the kind of the solvent; the greatest changes were observed in benzene‐d₆ and the smallest in CDCl₃. In acetone‐d₆ and DMSO‐d₆, the influence of substituents on chemical shifts is similar and the most regular. It allowed a fair correlation of chemical shifts of para‐substituted dibenzoylmethane derivatives' characteristic protons with Hammett substituent constants in these solvents. In CDCl₃, characteristic protons' chemical shifts were near ¹H NMR spectroscopy measurement error limits, and, therefore, correlation with Hammett substituent constants in this solvent was unsatisfactory. In benzene, although the changes of chemical shifts are the most evident, the changes are also the most irregular, and, therefore, correlation in this solvent failed completely. Results of meta‐substituted derivatives were much more irregular, and their correlation with Hammett substituent constants was poor in all investigated solvents. Copyright © 2013 John Wiley & Sons, Ltd.     

The thermodynamic limit of quantum Coulomb systems Part I. General theory

This article is the first in a series dealing with the thermodynamic properties of quantum Coulomb systems.In this first part, we consider a general real-valued function E defined on all bounded open sets of R³. Our aim is to give sufficient conditions such that E has a thermodynamic limit. This means that the limit E(Ωn)|Ωn|⁻¹ exists for all ‘regular enough’ sequence Ωn with growing volume, |Ωn|→∞, and is independent of the considered sequence.The sufficient conditions presented in our work all have a clear physical interpretation. In the next paper, we show that the free energies of many different quantum Coulomb systems satisfy these assumptions, hence have a thermodynamic limit.     

Thermal properties of solid complexes with biologically important heterocyclic ligands

The stoichiometry of thermal decomposition of the complexes Co(NCS)₂(fpy)₄ (I), Co(NCS)₂(Mefpy)₄ (II) and Co(NCS)₂(bfpy)₄ (III) (where fpy = furo[3,2-c]pyridine, Mefpy = methylfuro[3,2-c]pyridine, bfpy = benzo-[2, 3]furo[3,2-c]pyridine) have been investigated in nitrogen atmosphere from room temperature (RT) to 800 °C by means of TG and DTA. The results revealed that release of heterocyclic ligands occurs in one step. Infrared data suggested that fpy, Mefpy and bfpy were coordinated to Co(II) through the nitrogen atom of the respective heterocyclic ring and anionic ligands through nitrogen atom of the NCS groups.     

Simulated annealing and genetic algorithms for minimizing mean flow time in an open shop

This paper considers the problem of scheduling n jobs on m machines in an open shop environment so that the sum of completion times or mean flow time becomes minimal. It continues recent work by Bräsel et al. [H. Bräsel, A. Herms, M. Mörig, T. Tautenhahn, T. Tusch, F. Werner, Heuristic constructive algorithms for open shop scheduling to minmize mean flow time, European J. Oper. Res., in press (doi.10.1016/j.ejor.2007.02.057)] on constructive algorithms. For this strongly NP-hard problem, we present two iterative algorithms, namely a simulated annealing and a genetic algorithm. For the simulated annealing algorithm, several neighborhoods are suggested and tested together with the control parameters of the algorithm. For the genetic algorithm, new genetic operators are suggested based on the representation of a solution by the rank matrix describing the job and machine orders. Extensive computational results are presented for problems with up to 50 jobs and 50 machines, respectively. The algorithms are compared relative to each other, and the quality of the results is also estimated partially by a lower bound for the corresponding preemptive open shop problem. For most of the problems, the genetic algorithm is superior when fixing the same number of 30 000 generated solutions for each algorithm. However, in contrast to makespan minimization problems, where the focus is on problems with an equal number of jobs and machines, it turns out that problems with a larger number of jobs than machines are the hardest problems.     

Asymptotics of variance of the lattice point count

The variance of the number of lattice points inside the dilated bounded set rD with random position in ℝ ^d has asymptotics ∼ r ^d−1 if the rotational average of the squared modulus of the Fourier transform of the set is O(ϰ ^−d−1). The asymptotics follow from Wiener’s Tauberian theorem.     

Full analogy of Sharkovsky's theorem for lower semicontinuous maps

A full analogy of the celebrated Sharkovsky cycle coexistence theorem is established for lower semicontinuous (multivalued) maps on metrizable linear continua. This result is further extended to triangular maps.     

Modular Breath Analyzer (MBA): Introduction of a Breath Analyzer Platform Based on an Innovative and Unique,Modular eNose Concept for Breath Diagnostics and Utilization of Calibration Transfer Methods in Breath Analysis Studies

Exhaled breath analysis for early disease detection may provide a convenient method for painless and non-invasive diagnosis. In this work, a novel, compact and easy-to-use breath analyzer platform with a modular sensing chamber and direct breath sampling unit is presented. The developed analyzer system comprises a compact, low volume, temperature-controlled sensing chamber in three modules that can host any type of resistive gas sensor arrays. Furthermore, in this study three modular breath analyzers are explicitly tested for reproducibility in a real-life breath analysis experiment with several calibration transfer (CT) techniques using transfer samples from the experiment. The experiment consists of classifying breath samples from 15 subjects before and after eating a specific meal using three instruments. We investigate the possibility to transfer calibration models across instruments using transfer samples from the experiment under study, since representative samples of human breath at some conditions are difficult to simulate in a laboratory. For example, exhaled breath from subjects suffering from a disease for which the biomarkers are mostly unknown. Results show that many transfer samples of all the classes under study (in our case meal/no meal) are needed, although some CT methods present reasonably good results with only one class.