Seasonal indoor radon concentration in FYR of Macedonia

This paper presents the results of the seasonal indoor radon concentration measurements in dwellings in all regions of the Former Yugoslav Republic (FYR) of Macedonia. The measurements were made in 437 dwellings using CR-39 track detectors over four successive three-month periods (winter, spring, summer and autumn) throughout 2009. The results of analysis of variance showed statistically significant differences between indoor radon concentrations in different seasons. The geometric mean values and geometric standard deviations of indoor radon concentrations in winter, spring, summer and autumn were obtained to be: 115 Bq m^?3 (2.02), 72 Bq m^?3 (1.97), 46 Bq m^?3 (1.95), 92 Bq m^?3 (2.02), respectively. The geometric mean values of spring, summer and autumn to winter ratios were found to be: 0.63 (1.50), 0.40 (1.81), and 0.80 (1.58), respectively. The results of the analysis of the variance showed statistically significant differences among the indoor radon measurements for the regions in different seasons. The influence of the factors linked to building characteristics in relation to radon measurements in different seasons was examined. The factors which enable a differentiation into subgroups (significance level p < 0.05) are the floor level, basement and building materials.     

On the formation of hydrogen gas on copper in anoxic water

Hydrogen gas has been detected in a closed system containing copper and pure anoxic water [P. Szakalos, G. Hultquist, and G. Wikmark, Electrochem. Solid-State Lett. 10, C63 (2007) and G. Hultquist, P. Szakalos, M. Graham, A. Belonoshko, G. Sproule, L. Grasjo, P. Dorogokupets, B. Danilov, T. Aastrup, G. Wikmark, G. Chuah, J. Eriksson, and A. Rosengren, Catal. Lett. 132, 311 (2009)]. Although bulk corrosion into any of the known phases of copper is thermodynamically forbidden, the present paper shows how surface reactions lead to the formation of hydrogen gas in limited amounts. While water cleavage on copper has been reported and investigated before, formation of molecular hydrogen at a single-crystal Cu[100] surface is here explored using density functional theory and transition state theory. It is found that although solvent catalysis seems possible, the fastest route to the formation of molecular hydrogen is the direct combination of hydrogen atoms on the copper surface. The activation free energy (ΔG(s)(?)(f)) of hydrogen formation in condensed phase is 0.70 eV, which corresponds to a rate constant of 10 s(-1) at 298.15 K, i.e., a relatively rapid process. It is estimated that at least 2.4 ng hydrogen gas could form per cm(2) on a perfect copper surface.     

A Mössbauer spectroscopy study of polyol synthesized tavorite LiFeSO4F

The tavorite polymorph of LiFeSO₄F has attracted considerable attention as a cathode material for lithium ion batteries due to interesting structural and electrochemical characteristics. For the analysis of such iron-based electrode materials, Mössbauer spectroscopy has become an important and highly useful tool. In this work, we perform a detailed Mössbauer study of pristine tavorite LiFeSO₄F prepared by an optimized synthesis in tetraethylene glycol as reaction media. In contrast to many reported results, we demonstrate the use of an asymmetric fitting model for the inner doublet of the spectrum, which is coupled to the structural properties of the compound. Moreover, we discuss a new approach of ascribing the Fe^2?+?-doublets to the two distinct crystallographic iron sites of tavorite LiFeSO₄F by comparing the Mössbauer signal intensities with the expected f-factors for the corresponding iron atom.     

Adjoint Action of Automorphism Groups on Radical Endomorphisms,Generic Equivalence and Dynkin Quivers

Let Q be a connected quiver with no oriented cycles, k the field of complex numbers and P a projective representation of Q. We study the adjoint action of the automorphism group Aut _kQ P on the space of radical endomorphisms radEnd _kQ P. Using generic equivalence, we show that the quiver Q has the property that there exists a dense open Aut _kQ P-orbit in radEnd _kQ P, for all projective representations P, if and only if Q is a Dynkin quiver. This gives a new characterisation of Dynkin quivers.     

Supramolecular control in carbohydrate epimerization: discovery of a new anion host-guest system

A new anion-carbohydrate recognition system is described. Pyranosides with axial protons in 1-, 3-, and 5-position proved efficient, forming relatively strong complexes between the anion and the B-face of the carbohydrate. This system could furthermore be used in supramolecular control in Lattrell-Dax epimerization reactions, leading to either activation or deactivation effects.     

Mechanistic insights into the stepwise Diels-Alder reaction of 4,6-dinitrobenzofuroxan

The stepwise Diels-Alder reaction between 1-trimethylsiloxy-1,3-butadiene and 4,6-dinitrobenzofuroxan is explored using state-of-the-art computational methods. The results support a stepwise mechanism via a persistent intermediate, however, not the one previously reported (Lakhdar et al., Chem. Eur. J.2007, 16, 5681) but a heterocyclic adduct. The novel DFT functional M062X and the SCS-MP2 method were essential to reproduce a reasonable potential energy surface for this challenging system.     

Predicting regioselectivity in nucleophilic aromatic substitution

We have investigated practical and computationally efficient methods for the quantitative prediction of regioisomer distribution in kinetically controlled nucleophilic aromatic substitution reactions. One of the methods is based on calculating the relative stabilities of the isomeric σ-complex intermediates using DFT. We show that predictions from this method can be used quantitatively both for anionic nucleophiles with F(-) as leaving group, as well as for neutral nucleophiles with HF as leaving group. The σ-complex approach failed when the leaving group was Cl/HCl or Br/HBr, both for anionic and neutral nucleophiles, because of difficulties in finding relevant σ-complex structures. An approach where we assumed a concerted substitution step and used such transition state structures gave quantitatively useful results. Our results are consistent with other theoretical works, where a stable σ-complex has been identified in some cases, whereas others have been indicated to proceed via a concerted substitution step.