Analysis of organic compounds in environmental samples by headspace solid phase microextraction

The analysis of samples contaminated by organic compounds is an important aspect of environmental monitoring. Because of the complex nature of these samples, isolating target organic compounds from their matrices is a major challenge. A new isolation technique, solid phase microextraction, or SPME, has recently been developed in our laboratory. This technique combines the extraction and concentration processes into one step; a fused silica fiber coated with a polymer is used to extract analytes and transfer them into a GC injector for thermal desorption and analysis. It is simple, rapid, inexpensive, completely solvent-free, and easily automated. To minimize matrix interferences in environmental samples, SPME can be used to extract analytes from the headspace above the sample. The combination of headspace sampling with SPME separates volatile and semi-volatile analytes from non-volatile compounds, thus greatly reducing the interferences from non-target compounds. This paper reports the use of headspace SPME to isolate volatile organic compounds from various matrices such as water, sand, clay, and sludge. By use of the technique, benzene, toluene, ethyl-benzene, and xylene isomers (commonly known as BTEX), and volatile chlorinated compounds can be efficiently isolated from various matrices with good precision and low limits of detection. This study has found that the sensitivity of the method can be greatly improved by the addition of salt to water samples, water to soil samples, or by heating. Headspace SPME can also be used to sample semi-volatile compounds, such as PAHs, from complex matrices.     

Dipole,quadrupole, octupole,and dipole–octupole polarizabilities at real and imaginary frequencies for H,HE, and H2 and the dispersion-energy coefficients for interactions between them

We have calculated certain dynamic polarizabilities (for both real and imaginary frequencies) for H, He, and H₂ and the dispersion-energy coefficients for long-range interactions between them. We have done so in a sum-over-states formalism with explicitly electron-correlated wave functions to describe the states. To be precise, we have determined the dipole (α₁), quadrupole (α₂), and octupole (α₃) polarizabilities of H and He for real frequencies (ω) in a range between zero and the first electronic-transition frequency and for imaginary frequencies (iω) on a 32-point Gauss-Legendre grid running from zero to ?ω = 20 E_h, and for H₂, we have found the dipole (α), quadrupole (C), and dipole–octupole (E) polarizability tensors for the same real and imaginary frequencies. The dispersion-energy coefficients, obtained by combining the sum-over-states for-malism for the polarizabilities with analytic integration over ω, gave values of C₆, C₈, and C₁₀ for the atom–atom systems; C, C, C, C, and C for the atom–diatom systems; and C₆, C and C for the H₂? H₂ system. Nearly all the results are considered to be more reliable than those hitherto published and some have been obtained for the first time, e.g., C(iω), E(ω), and E(iω) for H₂ and C, C, and C for the H? H₂ system. © 1993 John Wiley & Sons, Inc.     

The transitional isoelectric focusing process

The transitional isoelectric focusing (IEF) process (the course of pH gradient formation by carrier ampholytes (CAs) and the correlation of the focusing time with CA concentration) were investigated using a whole-column detection capillary isoelectric focusing (CIEF) system. The transitional double-peak phenomenon in IEF was explained as a result of migration of protons from the anodic end and hydroxyl ions from the cathodic end into the separation channel and the higher electric field at both acidic and basic sides of the separation channel. It was observed that focusing times increase logarithmically with CA concentration under a constant applied voltage. The correlation of focusing time with CA concentration was explained by the dependence of the charge-transfer rate on the amount of charged CAs within the separation channel during focusing.     

Polonium 210Po activities in human blood of patients with ischaemic heart disease from Gdańsk in Poland

The determination of polonium ²¹⁰Po in human blood samples is presented and discussed in this paper. The human blood samples were collected from patients of Medical University of Gdańsk with ischaemic heart disease (morbus ischaemicus cordis, MIC). The polonium concentrations in analyzed human blood samples are very differentiated. ²¹⁰Po is of particular interest in public health and although is present in the environment in extremely low amounts, it is easily bioaccumulated to the human body. The study shows that the amount of ²¹⁰Po that is incorporated into the human body depends on the food habits and some difference in its levels could be observed between smokers and non-smokers.     

Interactive Multiple Criteria Decision Making based on preference driven Evolutionary Multiobjective Optimization with controllable accuracy

We present an approach to interactive Multiple Criteria Decision Making based on preference driven Evolutionary Multiobjective Optimization with controllable accuracy.The approach relies on formulae for lower and upper bounds on coordinates of the outcome of an arbitrary efficient variant corresponding to preference information expressed by the Decision Maker. In contrast to earlier works on that subject, here lower and upper bounds can be calculated and their accuracy controlled entirely within evolutionary computation framework. This is made possible by exploration of not only the region of feasible variants - a standard within evolutionary optimization, but also the region of infeasible variants, the latter to our best knowledge being a novel approach within Evolutionary Multiobjective Optimization.To illustrate how this concept can be applied to interactive Multiple Criteria Decision Making, two algorithms employing evolutionary computations are proposed and their usefulness demonstrated by a numerical example.     

Stepwise Stress-Induced Transformations of Metal-Organic Polyhedral Cluster-Based Assemblies: Where Conformational and Supramolecular Features Meet

Understanding the factors governing the formation of supramolecular structures and phase transitions between various forms of molecular crystals is pivotal for developing dynamic, stimuli-responsive materials and polymorph-controlled syntheses. Here, we investigate the pressure-induced dynamic of both the intrinsic molecular structure and the supramolecular network of a predesigned polyhedral oxo-centered zinc cluster incorporating monoanionic N,N’-diphenylformamidinate and featuring N-bonded phenyl groups in close proximity to the primary coordination sphere. We demonstrate that the model oxo cluster is prone to undergoing pressure-induced conformational transformations of the secondary coordination sphere and simultaneous stepwise (initially every second polyhedral molecule undergoes the conformational transformations) and reversible transitions from an ambient phase α to high-pressure phases β and γ, as single-crystal-to-single-crystal events. The observed phase transitions illustrate the key role of an interplay between the low-energy conformation perturbations and cooperative intra- and intermolecular noncovalent interactions.     

Impact of proliferation strategies on food web viability in a model with closed nutrient cycle

A food web model with a closed nutrient cycle is presented and analyzed via Monte Carlo simulations. The model consists of three trophic levels, each of which is populated by animals of one distinct species. While the species at the intermediate level feeds on the basal species, and is eaten by the predators living at the highest level, the basal species itself uses the detritus of animals from higher levels as the food resource. The individual organisms remain localized, but the species can invade new lattice areas via proliferation. The impact of different proliferation strategies on the viability of the system is investigated. From the phase diagrams generated in the simulations it follows that in general a strategy with the intermediate level species searching for food is the best for the survival of the system. The results indicate that both the intermediate and top level species play a critical role in maintaining the structure of the system.     

Fixed points of some nonlinear operators in spaces of multifunctions and the Ulam stability

We prove a fixed point theorem for nonlinear operators, acting on some function spaces (of set-valued maps), which satisfy suitable inclusions. We also show some applications of it in the Ulam type stability.     

[11]Anthrahelicene on TiO2 surfaces

Helicenes are carbon-rich materials with an ordered structure that possess interesting and remarkable electronic, chiroptical, mechanical and magnetic properties either in bulk or as single molecule devices. We report on the first attempt to anchor and organize [11]anthrahelicene ([11]AH) molecules onto a metal oxide surface. Molecular structures obtained on the (110) and (011) faces of rutile titania are characterized using scanning probe microscopy. On the (110) surface, [11]AH molecules form islands that are comprised of small domains of two types that are mirror reflections of each other and have an ordered quasi-hexagonal lattice. In contrast, molecules form unordered clusters on the (011) surface. Single molecules on both faces are imaged with sub-molecular resolution.     

Effectiveness of the Oxygenation over Classical Protonolysis Reactions: A Case of Alkylzinc Complexes Incorporating an Aminoalcoholate Ligand

Alkylzinc aminoalcoholates have emerged as powerful catalysts in organic synthesis and polymerization processes. Despite extensive research, difficulties in the rational design of these catalytic systems and in-depth understanding of their modes of action have hitherto been encountered. Most of the major obstacles stem largely from the relatively limited knowledge of the structure-activity relationship of zinc catalysts. In fact, the key active species are often generated in situ via the protonolysis of the alkylzinc precursors, which precludes their isolation and detailed characterization. Herein, the effectiveness of the oxygenation over the classical protonolysis in the synthesis of zinc alkylperoxides stabilized by an aminoalcoholate ligand is demonstrated. The controlled oxygenation of a tert-butylzinc complex incorporating a pridinolum (prinol) ligand leads to well-defined a dinuclear adduct of a (prinol)ZnOOtBu moiety with the parent tBuZn(prinol) complex and a novel dimer [tBuOOZn(prinol)]₂ with terminal alkylperoxide groups. The observed reaction outcomes strongly depend on the reaction conditions. Although sparse examples of heteroleptic adducts of the [RZn(L)]_x[ROOZn(L)]_y-type are known, the herein reported homoleptic [ROOZn(L)]_x aggregate is unprecedented. Strikingly, comparative studies involving reactions between tBuZn(prinol) and tert-butylhydroperoxide or ethanol revealed that the respective seemingly simple zinc alkylperoxides, or zinc alkoxides, respectively, are not accessible via the classical alcoholysis. We believe that these game-changing results concerning multifaceted chemistry of organozinc aminoalcoholates should pave the way for more rational development of various Zn-based catalytic systems.