Radioactivity measurements in epiphytic lichens of Uludağ Mountain in Western Anatolia

Activity concentrations of gross-β, naturally occurring ²²⁶Ra, ²³²Th, ²¹⁰Pb, ⁷Be and anthropogenic ¹³⁷Cs in epiphytic lichens collected from Uluda? Mountain are presented and discussed with the aim of evaluating potential usability of lichens as a biomonitor. The activity concentrations of gross-β, ¹³⁷Cs, ⁴⁰K, ²²⁶Ra, ²³²Th, ²¹⁰Pb and ⁷Be in the lichen samples were found to be in the range of 177–707, 4.05–94.26, 86–211, below detection limit (BDL)—19.2, BDL—14.0, 229–872, and 72.1–220.7 Bq kg^?1 in dry weight, respectively. ¹³⁷Cs content in collected epiphytic lichens was in descending order: Parmelia sulcata > Lobaria pulmonaria > Pseudevernia furfuracea > Usnea filipendula. The best biomonitor for ¹³⁷Cs among the lichen species used in this study was determined as Parmelia sulcata. Pearson’s correlation coefficient was calculated between ¹³⁷Cs and ⁴⁰K activity concentrations using a statistical package program (SPSS ver. 17.0) and a negative correlation value (R = ?0,323, p = 0,222) was obtained. The highest ²²⁶Ra and ²³²Th activity concentrations were found in Bo?azova Yaylas? which has a geological structure including granitic rocks. It was found that ¹³⁷Cs and ⁷Be activity concentrations in species demonstrated an inverse behaviour. The effect of mean annual precipitation and temperature on ⁷Be activity concentration was determined using multi regression analysis. Also, correlations between the ¹³⁷Cs and ⁷Be, and ⁴⁰K and ⁷Be were investigated.     

Substituent effects on the ring‐opening mechanism of gem‐dibromospiropentanes to related allenes: a theoretical study

Density functional theory computations at B3LYP and X3LYP levels were performed for ring openings of substituted gem‐dibromospiropentanes (R = ―H, ―Cl, ―Br, ―CH₃, ―SiH₃, ―OH, ―OCH₃, ―CF₃, ―BF₂, and ―SH) to related allenes. The conversion of spiropentanoids 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h , 5i , 5j to the corresponding allenes 7a , 7b , 7c , 7d , 7e , 7f , 7g , 7h , 7i , 7j can proceed in both concerted and stepwise mechanism except for R = ―H. Both ring‐opening mechanisms have similar activation energy barriers to open the spiropentanylidene ring and generate the structure of allene at all theoretical levels used herein. Generally the π electron‐donating group (―OH or ―SH) decreases the activation barrier for the follow‐up reaction of 1‐bromo‐1‐lithiospiropentanoid and free spiropentanylidene. Hence, both bearing electron‐donating substituents are more reactive than those with electron‐withdrawing group, and the first one to open the ring to the LiBr–allene complex does so more readily than the second. The sEDA index used to measure sigma‐electron excess/deficiency of the cyclopropylidene ring is mutually correlated for the studied systems. Copyright © 2015 John Wiley & Sons, Ltd.     

Equilibrium Formation of Stable All‐Silicon Versions of 1,3‐Cyclobutanediyl

Main group analogues of cyclobutane‐1,3‐diyls are fascinating due to their unique reactivity and electronic properties. So far only heteronuclear examples have been isolated. Here we report the isolation and characterization of all‐silicon 1,3‐cyclobutanediyls as stable closed‐shell singlet species from the reversible reactions of cyclotrisilene c‐Si₃Tip₄ (Tip=2,4,6‐triisopropylphenyl) with the N‐heterocyclic silylenes c‐[(CR₂CH₂)(NtBu)₂]Si: (R=H or methyl) with saturated backbones. At elevated temperatures, tetrasilacyclobutenes are obtained from these equilibrium mixtures. The corresponding reaction with the unsaturated N‐heterocyclic silylene c‐(CH)₂(NtBu)₂Si: proceeds directly to the corresponding tetrasilacyclobutene without detection of the assumed 1,3‐cyclobutanediyl intermediate.     

On a Modified Subgradient Algorithm for Dual Problems via Sharp Augmented Lagrangian*

We study convergence properties of a modified subgradient algorithm, applied to the dual problem defined by the sharp augmented Lagrangian. The primal problem we consider is nonconvex and nondifferentiable, with equality constraints. We obtain primal and dual convergence results, as well as a condition for existence of a dual solution. Using a practical selection of the step-size parameters, we demonstrate the algorithm and its advantages on test problems, including an integer programming and an optimal control problem. *Partially Supported by 2003 UniSA ITEE Small Research Grant Ero2. Supported by CAPES, Brazil, Grant No. 0664-02/2, during her visit to the School of Mathematics and Statistics, UniSA.     

Renal-related perinephric fluid collections: MRI findings

We retrospectively reviewed MR studies on 10 patients with renal-related perinephric fluid collections who underwent MRI in three institutions between January 2001 and August 2004. All patients underwent MRI of the abdomen and T1-weighted, T2-weighted and serial contrast-enhanced images, including delayed-phase contrast-enhanced images 10-12 min after contrast injection, were obtained. Perinephric fluid collections in 5 patients revealed MRI findings of simple fluid content (i.e., hypointense on T1-weighted images and hyperintense on T2-weighted images). In another 5 patients, a complex perinephric fluid content (i.e., mixed hyper/hypointense on T1-weighted images and mixed hypo/hyperintense on T2-weighted images compatible with blood breakdown products and pus) was observed. In 5 patients, contrast extravasation on late-phase images that was compatible with urine leak was demonstrated. Our results suggest that MRI may determine the content of perinephric fluid collections on noncontrast T1-weighted and T2-weighted images and that contrast extravasation on late-phase images is associated with urine extravasation from renal collecting systems.     

Redox equilibria of iron oxides in aqueous-based magnetite dispersions: effect of pH and redox potential

The effect of pH and redox potential on the redox equilibria of iron oxides in aqueous-based magnetite dispersions was investigated. The ionic activities of each dissolved iron species in equilibrium with magnetite nanoparticles were determined and contoured within the Eh-pH framework of a composite stability diagram. Both standard redox potentials and equilibrium constants for all major iron oxide redox equilibria in magnetite dispersions were found to differ from values reported for noncolloidal systems. The "triple point" position of redox equilibrium among Fe(II) ions, magnetite, and hematite shifted to a higher standard redox potential and an equilibrium constant which was several orders of magnitude higher. The predominant area of magnetite stability was enlarged to cover a wider range of both pH and redox potentials as compared to that of a noncolloidal magnetite system.     

Synthesis in water-free DMF, characterization, electrical, and gas sensing properties of bis[2-(2-aminoethylamino)ethanol]copper(II) dibromide

2-(2-Aminoethylamino)ethanol (L) reacts with cupric bromide in dimethylformamide to give a mononuclear complex of Cu(II) [L₂Cu]Br₂, with six-coordinate distorted octahedral geometry, in which two molecules of tridentate (N,N,O) ligand are involved. The structure was confirmed by spectroscopic methods, elemental and thermogravimetric analyses, and magnetic measurements. Optimization of possible configurations indicated the formation of the trans structure of the complex. Experimental results indicate that the investigated complex, bis[2-(2-aminoethylamino)ethanol] copper(II) bromide, behaves as a semiconductor in the studied temperature range of 298–388 K. Gas sensing properties of the film for the volatile organic compounds (VOCs): acetone, tetra-chloromethane, chloroform, ethanol, and methanol, were also investigated as a function of vapor concentration and temperature in dark. The film showed maximum sensitivity to tetrachloromethane and ethanol vapors at room temperature. Responses of the film to the tested gases are reversible.     

The synthesis and characterization of copper(II)–<Emphasis Type="Italic">p</Emphasis>-aminosalicylate complexes with diamine ligands

The complexes were synthesized by the reaction between sodium salt of p-aminosalicylic acid (PAS) and Cu(II) for 1 and corresponding ethylenediamine (en) or its derivatives for 2–6. The complexes were characterized by using elemental analyses, FT-IR, UV–Vis, magnetic moment measurements, and thermal analyses techniques. In complex 1[Cu₂(PA)₄(H₂O)₂], two Cu(II) ions were found as bridged by four μ-O:O′ p-aminosalicylato (PA) ligands, forming a cage structure, and two aqua ligands to form dinuclear square-pyramidal geometry around Cu(II) ions. In the complexes 2–6, the PA (anionic form of p-aminosalicylic acid) coordinated to Cu(II) ions as monodentate manner by using its oxygen atom of deprotonated carboxylic acid and ethylenediamine derivatives coordinated to the Cu(II) ions in bidentate manner to form mononuclear octahedral complexes [Cu(PA)₂(L)₂] (L = ethylendiamine, N,N-dimethylethylendiamine, N,N′-dimethylethylendiamine, N,N,N′,N′-tetramethylethylendiamine, and 1,3-propanediamine, for complexes 2, 3, 4, 5, and 6, respectively). In all the complexes OH and NH₂ groups of PA ligands were not coordinated to metals.     

Immersed boundary method for unsteady kinetic model equations

Predicting unsteady flows and aerodynamic forces for large displacement motion of microstructures requires transient solution of Boltzmann equation with moving boundaries. For the inclusion of moving complex boundaries for these problems, three immersed boundary method flux formulations (interpolation, relaxation, and interrelaxation) are presented. These formulations are implemented in a 2‐D finite volume method solver for ellipsoidal‐statistical (ES)‐Bhatnagar‐Gross‐Krook (BGK) equations using unstructured meshes. For the verification, a transient analytical solution for free molecular 1‐D flow is derived, and results are compared with the immersed boundary (IB)‐ES‐BGK methods. In 2‐D, methods are verified with the conformal, non‐moving finite volume method, and it is shown that the interrelaxation flux formulation gives an error less than the interpolation and relaxation methods for a given mesh size. Furthermore, formulations applied to a thermally induced flow for a heated beam near a cold substrate show that interrelaxation formulation gives more accurate solution in terms of heat flux. As a 2‐D unsteady application, IB/ES‐BGK methods are used to determine flow properties and damping forces for impulsive motion of microbeam due to high inertial forces. IB/ES‐BGK methods are compared with Navier–Stokes solution at low Knudsen numbers, and it is shown that velocity slip in the transitional rarefied regime reduces the unsteady damping force. Copyright © 2015 John Wiley & Sons, Ltd.     

Composition,properties, and application of products formed in oxidation of polyethylene by nitric acid

Structure of products formed in polyethylene oxidation by nitric acid was studied by NMR, IR, and electronic absorption spectroscopies and derivatography.