Determination of Henry''s law coefficients by combination of the equilibrium partitioning in closed systems and solid-phase microextraction techniques

This paper describes the determination of Henry's law coefficients by means of the EPICS (equilibrium partitioning in closed systems) technique in combination with SPME (solid-phase microextraction). The use of solid-phase microextraction-sampling allowed us to extend the possibilities of the equilibrium partitioning in closed systems technique with respect to the range of Henry's law coefficients which can be measured. Whereas the equilibrium partitioning in closed systems technique is limited to determine air–water equilibrium partitioning of volatile compounds with Henry's law coefficients of at least 0.06 (dimensionless), the current method allowed to measure coefficients between 0.0023 and 13.5. In this way Henry's law coefficients of 20 compounds, being in a range covering five orders of magnitude, were measured with relative standard deviations between 1.0 and 19.8% (mean standard deviation: 5.7%; median of standard deviations: 4.8%, n=99). Several types of compounds were examined i.e. aliphatic hydrocarbons, monocyclic and polycyclic aromatic hydrocarbons, chlorinated and fluorinated compounds, ethers and esters, biphenyl and N-containing compounds, including compounds for which availability of experimental Henry's law coefficients is limited. Measurement of the equilibrium partitioning in the 2 to 25°C range allowed to establish relations of Henry's law coefficient as a function of temperature.     

Effect of PBT molecular weight and reactive compatibilization on the dispersed‐phase coalescence of PBT/SAN blends

Poly(butylene terephthalate) (PBT)/styrene‐acrylonitrile copolymer (SAN) blends were investigated with respect to their phase morphology. The SAN component was kept as dispersed phase and PBT as matrix phase and the PBT/SAN viscosity ratio was changed by using different PBT molecular weights. PBT/SAN blends were also compatibilized by adding methyl methacrylate‐co‐glycidyl methacrylate‐co‐ethyl acrylate terpolymer, MGE, which is an in situ reactive compatibilizer for melt blending. In noncompatibilized blends, the dispersed phase particle size increased with SAN concentration due to coalescence effects. Static coalescence experiments showed evidence of greater coalescence in blends with higher viscosity ratios. For noncompatibilized PBT/SAN/MGE blends with high molecular weight PBT as matrix phase, the average particle size of SAN phase does not depend on the SAN concentration in the blends. However noncompatibilized blends with low molecular weight PBT showed a significant increase in SAN particle size with the SAN concentration. The effect of MGE epoxy content and MGE molecular weight on the morphology of the PBT/SAN blend was also investigated. As the MGE epoxy content increased, the average particle size of SAN initially decreased with both high and low molecular weight PBT phase, thereafter leveling off with a critical content of epoxy groups in the blend. This critical content was higher in the blends containing low molecular weight PBT than in those with high molecular weight PBT. At a fixed MGE epoxy content, a decrease in MGE molecular weight yielded PBT/SAN blends with dispersed nanoparticles with an average size of about 40 nm. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

FRACTOP: A Geometric Partitioning Metaheuristic for Global Optimization

We propose a new metaheuristic, FRACTOP, for global optimization. FRACTOP is based on the geometric partitioning of the feasible region so that search metaheuristics such as Simulated Annealing (SA), or Genetic Algorithms (GA) which are activated in smaller subregions, have increased reliability in locating the global optimum. FRACTOP is able to incorporate any search heuristic devised for global optimization. The main contribution of FRACTOP is that it provides an intelligent guidance (through fuzzy measures) in locating the subregion containing the global optimum solution for the search heuristics imbedded in it. By executing the search in nonoverlapping subregions, FRACTOP eliminates the repetitive visits of the search heuristics to the same local area and furthermore, it becomes amenable for parallel processing. As FRACTOP conducts the search deeper into smaller subregions, many unpromising subregions are discarded from the feasible region. Thus, the initial feasible region gains a fractal structure with many space gaps which economizes on computation time. Computational experiments with FRACTOP indicate that the metaheuristic improves significantly the results obtained by random search (RS), SA and GA.     

First description of B chromosomes in the family Auchenipteridae,Parauchenipterus galeatus (Siluriformes) of the São Francisco River basin (MG,Brazil)

B chromosomes are considered additional and non-essential; they likely originate from A chromosomes and follow a distinct evolution. In fish, approximately half of the Neotropical species with B chromosomes are Characiformes and 35% are Siluriformes. There has been no report of B chromosomes in Auchenipteridae until this moment. B chromosomes found in a population of Parauchenipterus galeatus from the São Francisco River basin in the state of Minas Gerais (Brazil) were small, metacentric, totally heterochromatic and exhibited intra-individual and inter-individual variation. The diploid number was 58 chromosomes (22 metacentric, 16 submetacentric, 12 subtelocentric and 8 acrocentric). The nucleolar organizing regions were simple and the heterochromatin intercalated in the ribosomal sites, characterized by CMA₃ and DAPI fluorochromes, was of a GC-rich constitution. The 5S rDNA genes were located in an intercalary position in only one chromosome pair. An hypothesis about the origin of the B chromosomes in P. galeatus and a review on B chromosomes in catfish are also presented in this study.     

Crystal Structure of Bis -(2,2′-bipyridine-N,N′)-(dicyanamide-N)-copper(II) Tricyanomethanide. Electronic and Structural Parameters Describing the Shape of Coordination Polyhedra in Five-Coordinated Copper(II) Compounds

 The structure of the new compound [Cu(bpy)₂N(CN)₂]C(CN)₃ (6) is compared with thestructures of six copper(II) coordination compounds with phenanthroline or bipyridine ligands and N-donor pseudohalide anions: [Cu(phen)₂NCS]C(CN)₃ (1), [Cu(bpy)₂NCS]C(CN)₃ (2), [Cu(phen)₂NCS]ONC(CN)₂ (3), [Cu(phen)₂N(CN)₂]C(CN)₃ (4), [Cu(bpy)₂C(CN)₃]C(CN)₃ (5), and [Cu(bpy)₂NCO]C(CN)₃ (7). The Cu(II) atoms in all above compounds are five-coordinated with an N-donor atom of the pseudohalide anion located in the equatorial plane of a deformed trigonal bipyramid. The shape of the coordination polyhedra and the degree of trigonal bipyramidal distortion towards a tetragonal pyramid are discussed and described using one electronic and several structural criteria which are discussed and compared.     

Solid State Amorphisation in Magnetic Multilayers: the Interface Structure and the Electrical Transport Properties

The structure and electrical conductivity properties of the R.F. sputtered FeZr and FeTi multilayers with ultrathin layer thicknesses, in as-deposited states, have been studied using X-ray diffraction, low-angle X-ray and neutron reflectometry, conversion electron Mössbauer spectroscopy (CEMS), resistivity and magnetoresistivity measurements. The thickness ratio (β=d_Fed_Zr and d_Fed_Ti) of analysed multilayers was 0.5 and 1, the values of the bilayer thickness (λ=d_Fe+d_Ti,Zr) was varied from 9 Å to 600 Å, maintaining constant the total thickness of the samples by controlling the number of bilayers. The results obtained from CEM-spectroscopy and X-ray diffraction show that Fe layers of the thickness below 20 Å are alloyed forming an amorphous phase during deposition. This amorphous phase is distributed in the plane between the crystalline sublayers as well as in the grain boundaries according with the proposed model of the interpretation of the electrical conductivity as a function of the bilayer thickness (λ).     

Chirped fibre Bragg grating based multiplexer and demultiplexer for DWDM applications

A multiplexer/demultiplexer for 100 GHz channel spacing based on chirped fibre Bragg gratings with different bandwidths and optical circulators is presented. The spectral characteristics, specifications and operation of these passive devices are described, showing its potential use in dense wavelength division multiplexing (DWDM) applications.