Sturm-Liouville operators with indefinite weight functions and eigenvalue depending boundary conditions

We consider a class of boundary value problems for Sturm-Liouville operators with indefinite weight functions. The spectral parameter appears nonlinearly in the boundary condition in the form of a function τ which has the property that λ?λτ(λ) is a generalized Nevanlinna function. We construct linearizations of these boundary value problems and study their spectral properties.     

A computational and experimental study of the structures and Raman and 77Se NMR spectra of SeX3+ and SeX2 (X = Cl, Br, I): FT-Raman spectrum of (SeI3)[AsF6

The ability of MP2, B3PW91 and PBE0 methods to produce reliable predictions in structural and spectroscopic properties of small selenium-halogen molecules and cations has been demonstrated by using 6-311G(d) and cc-pVTZ basis sets. Optimized structures and vibrational frequencies agree closely with the experimental information, where available. Raman intensities are also well reproduced at all levels of theory. Calculated GIAO isotropic shielding tensors yield a reasonable linear correlation with the experimental chemical shift data at each level of theory. The largest deviations between calculated and experimental chemical shifts are found for selenium-iodine species. The agreement between observed and calculated chemical shifts for selenium-iodine species can be improved by inclusion of relativistic effects using the ZORA method. The best results are achieved by adding spin-orbit correction terms from ZORA calculations to nonrelativistic GIAO isotropic shielding tensors. The calculated isotropic shielding tensors can be utilized in the spectroscopic assignment of the 77Se chemical shifts of novel selenium-halogen molecules and cations. The experimental FT-Raman spectra of (SeI3)[AsF6] in the solid state and in SO2(l) solution are also reported.     

Atom based parametrization for a conformationally dependent hydrophobic index

An atomic parametrization for the determination of a hydrophobicity index that depends on the molecular conformation is presented. The hydrophobicity parameter was calculated in four alternative ways based on charge densities and atomic contributions to the total molecular surface area and depending on the approach, the molecular dipole moment. The geometries required for the computations were calculated using quantum mechanical semiempirical methods as well as molecular mechanics. The charges were computed using semiempirical methods as well as the Gasteiger method.     

Polymorphism in Cs[AgZn(NCS)4]

The title compound, caesium silver zinc tetrathiocyanate, crystallizes in two polymorphic forms, in space groups P2₁/n and C2/c. Both structures form a continuous three‐dimensional network. The structure in C2/c contains a delocalized Ag atom in a binuclear‐like anion, where two [Ag(NCS)₄] units (delocalized Ag as an average) share two common NCS^? ligands.     

Electrochemical detection of microcystins, cyanobacterial peptide hepatotoxins, following high-performance liquid chromatography

A novel amperometric HPLC detection method for the cyanobacterial (blue–green algal) peptide toxins microcystin-LR, -YR and -RR was developed. Purified microcystins and cyanobacterial extracts were chromatographed using an internal surface reversed-phase column with acetate- and phosphate-based mobile phase systems. Electrochemical oxidation reactions at 1.20 V vs. Ag/AgCl (glassy carbon working electrode) were shown to originate in arginine and tyrosine residues of microcystins.     

Experimental and theoretical investigations of structural trends for selenium(IV) imides and oxides: X-ray structure of Se3(NAd)2

The thermal decomposition of Se(NAd)(2) (Ad = 1-adamantyl) in THF was monitored by (77)Se NMR and shown to give the novel cyclic selenium imide Se(3)(NAd)(2) as one of the products. An X-ray structural determination showed that Se(3)(NAd)(2) is a puckered five-membered ring with d(Se-Se) = 2.404(1) A and |d(Se-N)| = 1.873(4) A. On the basis of (77)Se NMR data, other decomposition products include the six-membered ring Se(3)(NAd)(3), and the four-membered rings AdNSe(micro-NAd)(2)SeO and OSe(micro-NAd)(2)SeO. The energies for the cyclodimerization of E(NR)(2) and RNEO (E = S, Se; R = H, Me, (t)Bu, SiMe(3)), and the cycloaddition reactions of RNSeO with E(NR)(2), RNSO(2) with Se(NR)(2), and S(NR)(2) with Se(NR)(2) have been calculated at MP2, CCSD, and CCSD(T) levels of theory using the cc-pVDZ basis sets and B3PW91/6-31G* optimized geometries. Sulfur(IV) and selenium(IV) diimide monomers are predicted to be stable, the sole exception being Se(NSiMe(3))(2) that shows a tendency toward cyclodimerization. The cyclodimerization energy for RNSeO and the cycloaddition reaction energies of RNSeO with Se(NR)(2) as well as that of RNSO(2) with Se(NR)(2) are negative, consistent with the observed formation of OSe(micro-N(t)Bu)(2)SeO, OSe(micro-N(t)Bu)(2)SeN(t)Bu, and O(2)S(micro-N(t)Bu)(2)SeN(t)Bu, respectively. Cycloaddition is unlikely when one of the reactants is a sulfur(IV) diimide.     

Target training with soft computing tools

The personal capabilities and intentions of employees indicate their performance within their organization. It is important for the organization to capture this kind of tacit knowledge since the workforce are the true experts in perceiving the organization's current reality and evaluating which assets require development – including themselves as knowledge assets. The collective inner voice of the workforce helps the organization's management to steer the company and its assets in a sustainable direction.This article presents how the collective inner voice of the workforce can be captured and how it can be used for the benefit of the organization and its employees. The objective is to support individuals’ personal aspirations, as well as to save the money, time and resources that an organization spends on personnel training.The focus of this article is on demonstrating a possible soft-computing method used for competency simulation. The process starts with a linguistic self-evaluation conducted by employees, where individuals’ own perception of current and target competence levels is captured. The self-evaluation is conducted with the help of fuzzy logic. Clusters are formed from the result dataset using an unsupervised neural network clustering method: self-organizing maps. A demonstrator tool is then used to perform a “what-if” type of analysis/simulation on the clusters in the results. With the demonstrator tool, employees can roughly test the impact of alternative training scenarios for themselves. For individuals this may open up new directions for self-development, and for organizations this may allow the efficient use of training resources. We tested the approach with a dataset from a real human resource development project among nuclear power plant operators.The case study reveals the potential of soft-computing based collective competency simulation as one part of personnel development projects in the future. Yet the techniques and the demonstrator tool used in this experiment are far from being products that employees could easily use as part of their training project. Possible benefits of the proposed approach are demonstrated in this article.     

Frequency distribution, isotopic composition and physical characterization of plutonium-bearing particles from the Fig-Quince zone on Runit Island, Enewetak Atoll

Runit Island on Enewetak Atoll was very heavily impacted by the U.S. nuclear testing campaign in the northern Marshall Islands (1946–58). The primary source of contamination on Runit Island was the 1958 Quince safety test where a large quantity of device plutonium (Pu) was scattered over the area near the GZ. A second low-yield device was detonated on the same site 10 days later, further disturbing the soil and leaving behind a very heterogeneous pattern of contamination including milligram-size particles of plutonium. A limited cleanup of the Fig-Quince zone was carried out in 1979. During this period, the effectiveness of the cleanup operations was primarily evaluated on the basis of bulk soil concentration data with little consideration given to the heterogeneity and long-term material-, biological-, and environmental-specific impacts of residual high activity (hot) particle contamination. The aim of the present study was twofold; (i) to characterize the levels and distribution of residual contamination in the Fig-Quince zone, and (ii) to develop pertinent data on the frequency distribution, elemental and isotopic composition, and physico-chemical properties of hot particles isolated from surface soils from Fig-Quince with a view towards providing recommendations on the future management and possible cleanup of the site. Today, Runit Island remains under an administrative quarantine.     

Thermo-Reversible Cellulose Micro Phase-Separation in Mixtures of Methyltributylphosphonium Acetate and γ-Valerolactone or DMSO

We have identified cellulose solvents, comprised of binary mixtures of molecular solvents and ionic liquids that rapidly dissolve cellulose to high concentration and show upper-critical solution temperature (UCST)-like thermodynamic behaviour - upon cooling and micro phase-separation to roughly spherical microparticle particle-gel mixtures. This is a result of an entropy-dominant process, controllable by changing temperature, with an overall exothermic regeneration step. However, the initial dissolution of cellulose in this system, from the majority cellulose I allomorph upon increasing temperature, is also exothermic. The mixtures essentially act as ‘thermo-switchable’ gels. Upon initial dissolution and cooling, micro-scaled spherical particles are formed, the formation onset and size of which are dependent on the presence of traces of water. Wide-angle X-ray scattering (WAXS) and ¹³C cross-polarisation magic-angle spinning (CP-MAS) NMR spectroscopy have identified that the cellulose micro phase-separates with no remaining cellulose I allomorph and eventually forms a proportion of the cellulose II allomorph after water washing and drying. The rheological properties of these solutions demonstrate the possibility of a new type of cellulose processing, whereby morphology can be influenced by changing temperature.