Raman and FTIR spectra of [Cu(H2O)6](BrO3)2 and [Al(H2O)6](BrO3)3 · 3H2O

Raman and FTIR spectra of [Cu(H2O)6](BrO3)2 and [Al(H2O)6](BrO3)3 · 3H2O are recorded and analyzed. The observed bands are assigned on the basis of BrO3 − and H2O vibrations. Additional bands obtained in the region of 3 and 1 modes in [Cu(H2O)6](BrO3)2 are due to the lifting of degeneracy of 3 modes, since the BrO3 − ion occupies a site of lower symmetry. The appearance 1 mode of BrO3 − anion at a lower wavenumber (771 cm−1) is attributed to the attachment of hydrogen to the BrO3 − anion. The presence of three inequivalent bromate groups in the [Al(H2O)6](BrO3)3 · 3H2O structure is confirmed. The lifting of degeneracy of 4 mode indicates that the symmetry of BrO3 − anion is lowered in the above crystal from C3v to C1. The appearance of additional bands in the stretching and bonding mode regions of water indicates the presence of hydrogen bonds of different strengths in both the crystals. Temperature dependent Raman spectra of single crystal [Cu(H2O)6](BrO3)2 are recorded in the range 77–523 K for various temperatures. A small structural rearrangement takes place in BrO3 − ion in the crystal at 391 K. Hydrogen bounds in the crystal are rearranging themselves leading to the loss of one water molecule at 485 K. This is preceded by the reorientation of BrO3 − ions causing a phase transition at 447 K. Changes in intensities and wavenumbers of the bands and the narrowing down of the bands at 77 K are attributed to the settling down of protons into ordered positions in the crystal

The electronic structure of anionic halide complexes of element 105 in aqueous solutions and their extraction by aliphatic amines

To study the complex formation of group 5 elements (Nb, Ta, Ha, and pseudoanalog Pa) in aqueous HCI solutions of medium and high concentrations the electronic structures of anionic complexes of these elements [MCl_6]^-, [MOCl_4]^-, [M(OH)-2 Cl_4]^-, and [MOCl_5]^2- have been calculated using the relativistic Dirac-Slater Discrete-Variational Method. The charge density distribution analysis has shown that tantalum occupies a specific position in the group and has the highest tendency to form the pure halide complex, [TaCl_6-. This fact along with a high covalency of this complex explains its good extractability into aliphatic amines. Niobium has equal trends to form pure halide [NbCl_6]^- and oxyhalide [NbOCl_5]^2- species at medium and high acid concentrations. Protactinium has a slight preference for the [PaOCl_5]^2- form or for the pure halide complexes with coordination number higher than 6 under these conditions. Element 105 at high HCl concentrations will have a preference to form oxyhalide anionic complex [HaOCl_5]^2- rather than [HaCl_6]^-. For the same sort of anionic oxychloride complexes an estimate has been done of their partition between the organic and aqueous phases in the extraction by aliphatic amines, which shows the following succession of the partition coefficients: P_Nb < P_Ha < P_Pa.

The Influence of Adjacent Segment on the Reliability of Cu Dual Damascene Interconnects

Three terminal ‘dotted-I’ interconnect structures, with vias at both ends and an additional via in the middle, were tested under various test conditions. Mortalities (failures) were found in right segments with jL value as low as 1250 A/cm, and the mortality of a dotted-I segment is dependent on the direction and magnitude of the current in the adjacent segment. Some mortalities were also found in the right segments under a test condition where no failure was expected. Cu extrusion along the delaminated Cu/Si₃N₄ interface near the central via region was believed to cause the unexpected failures. From the time-to-failure (TTF), it is possible to quantify the Cu/Si₃N₄ interfacial strength and bonding energy. Hence, the demonstrated test methodology can be used to investigate the integrity of the Cu dual damascene processes. As conventionally determined critical jL values in two-terminal via-terminated lines cannot be directly applied to interconnects with branched segments, this also serves as a good methodology to identify the critical effective jL values for immortality.

Comparison of subcellular partitioning, distribution, and internal speciation of Cu between Cu-tolerant and naive populations of Dendrodrilus rubidus Savigny

When considering contaminated site ecology and ecological risk assessment a key question is whether organisms that appear unaffected by accumulation of contaminants are tolerant or resistant to those contaminants. A population of Dendrodrilus rubidus Savigny earthworms from the Coniston Copper Mines, an area of former Cu mining, exhibit increased tolerance and accumulation of Cu relative to a nearby non-Cu exposed population. Distribution of total Cu between different body parts (posterior, anterior, body wall) of the two populations was determined after a 14 day exposure to 250 mg Cu kg(-1) in Cu-amended soil. Cu concentrations were greater in Coniston earthworms but relative proportions of Cu in different body parts were the same between populations. Cu speciation was determined using extended X-ray absorption fine structure spectroscopy (EXAFS). Cu was coordinated to 0 atoms in the exposure soil but to S atoms in the earthworms. There was no difference in this speciation between the different earthworm populations. In another experiment earthworms were exposed to a range of Cu concentrations (200-700 mg Cu kg(-1)). Subcellular partitioning of accumulated Cu was determined. Coniston earthworms accumulated more Cu but relative proportions of Cu in the different fractions (cytosol > granular > tissue fragments, cell membranes, and intact cells) were the same between populations. Results suggest that Coniston D. rubidus are able to survive in the Cu-rich Coniston Copper Mines soil through enlargement of the same Cu storage reservoirs that exist in a nearby non-Cu exposed population.

Effect of organic complexation on the toxicity of Cu to the earthworm Eisenia fetida

The relationship between Cu speciation in solution and mortality and tissue Cu concentrations in Eisenia fetida was investigated. E. fetida were exposed to solutions containing 0.009, 0.049 and 0.125 mg Cu L-1 and 0, 0.15, 0.35 and 50 mg EDTA L-1. Mortalities of 100, 60, 50 and 25% were recorded in the 0.125 mg Cu L-1 solutions containing 0, 0.15, 0.35 and 50 mg EDTA L-1, respectively. Similarly tissue body burden decreased with increasing EDTA concentration. Complexation capacity of the solution increased with EDTA concentration. In the 0.125 mg Cu L-1 solution labile Cu concentration decreased with increasing EDTA concentration. These trends are attributed to complexation of free Cu ions with EDTA molecules, and the non-bioavailable nature of the resultant Cu-EDTA complex. (C) 2007 Elsevier Ltd. All rights reserved.

Solvent Effects on the Formation of Nanoparticles and Multilayered Coatings Based on Hydrogen-Bonded Interpolymer Complexes of Poly(acrylic acid) with Homo- and Copolymers of N-Vinyl Pyrrolidone

The formation of hydrogen-bonded interpolymer complexes between poly(acrylic acid) and poly(N-vinyl pyrrolidone) as well as amphiphilic copolymers of N-vinyl pyrrolidone with vinyl propyl ether has been studied in aqueous and organic solutions. It was demonstrated that introduction of vinyl propyl ether units into the macromolecules of the nonionic polymer enhances their ability to form complexes in aqueous solutions due to more significant contribution of hydrophobic effects. The complexation was found to be a multistage process that involves the formation of primary polycomplex particles, which further aggregate to form spherical nanoparticles. Depending on the environmental factors (pH, solvent nature), these nanoparticles may either form stable colloidal solutions or undergo further aggregation, resulting in precipitation of interpolymer complexes. In organic solvents, the intensity of complex formation increases in the following order: methanol < ethanol < isopropanol < dioxane. The multilayered coatings were developed using layer-by-layer deposition of interpolymer complexes on glass surfaces. It was demonstrated that the solvent nature affects the efficiency of coating deposition.

Synthesis and evaluation of novel boron-containing complexes of potential use for the selective treatment of malignant melanoma

Boron-containing complexes that have the potential to irreversibly accumulate in melanoma cells have been prepared by reaction of amino acids with 9-methoxy-9-borabicyclo[3.3.1]nonane. The ability of each complex to act as a substrate for tyrosinase has been probed by oximetry. Increased uptake of the lead candidate in a tyrosinase-rich cell line, compared with a tyrosinase-absent cell line, is reported, with results correlating well with that for a drug currently approved for BNCT.

Endgame table testing of studies - II

The van der Heijden Studies Database (Version III) has been reviewed to identify 'Win Studies' with sub-7-man positions in the main line which are not wins for White. Some studies were faulted, A number for the first time: 21 of the more interesting escapes by Black are highlighted, themed and discussed.