Partition coefficients of environmentally important phenols in a supercritical carbon dioxide-water system from cocurrent extraction without analysis of the compressible phase

Partition coefficients of phenol, salicylic acid, and several environmentally important chloro- and nitrophenols in a supercritical CO2-water system were measured using direct cocurrent extraction of aqueous solutions of the individual solutes with CO2. Partitioning data on the nitrophenols and salicylic acid were obtained for the first time. To bypass the troublesome and error-prone analysis of the CO2-rich phase, the present method employed only the solute concentrations in the aqueous phase before and after extraction to determine the partition coefficient. Unlike most previous engineering studies of phenol partitioning in a CO2-water system, the concentrations of phenolic solutes approached infinite dilution in both phases. This makes the results relevant to analytical-scale SFE of environmental water samples with CO2. Because of effective infinite dilution of the solutes, the partition coefficients provide a direct measure of relative CO2-philicity/hydrophilicity of the individual phenols. Compared to the octanol-water partition coefficients of substituted phenols, the CO2-water partition coefficients are more sensitive to substitution in the position neighboring the hydroxyl group.     

Cross-property connections for copper–graphite composites

Copper–graphite composite materials in the range of 0–10 vol% of carbon phase were prepared from the mixture of copper and graphite powders by hot isostatic pressing. The microstructure, mechanical (tensile strength, elongation to fracture) and physical (electrical and thermal conductivity) properties of composite samples were investigated, and the cross-property connections were calculated. It was shown that electrical and thermal conductivity cross-property (Lorenz number) is almost constant and increases only slightly (no more than 10 % increase was observed). This implies that in the investigated composition range the Lorenz number of a copper–graphite composite system behaves according to Franz–Wiedemann law for pure metals at constant temperature. On the contrary, the conductivity to tensile strength cross-property connections showed significant linear increase (over 200 % in the investigated composition range) for both electrical conductivity and thermal conductivity of composite materials. The cross-property connections of conductivity to the elongation to fracture exhibit a nonlinear dependence on the volume fraction of graphite.     

Mechanochemical synthesis of ternary chalcogenide chalcostibite CuSbS2 and its characterization

Journal of Materials Science: Materials in Electronics - In this work, the very rapid one-step mechanochemical synthesis of nanocrystalline ternary chalcogenide chalcostibite CuSbS2 prepared from...     

A novel multiscale approach to brittle fracture of nano/micro‐sized components

Principles and advantages of a new concept based on the ab initio aided strain gradient elasticity theory are shown in comparison with the classical Barenblatt cohesive model. The method is applied to the theoretical prediction of the critical energy release rate and the crack tip opening displacement at the crack instability in nanopanels made of germanium and molybdenum crystals. The necessary length scale parameter l₁ is determined for germanium and molybdenum by the best gradient elasticity fits of ab initio computed screw dislocation displacements and phonon dispersions. Values of ab initio computed critical energy release rates and crack opening profiles revealed that the length l₁ is related to inflexion points of profiles. A novel ab initio method in combination with continuum mechanics was successfully tested to replace molecular statics dependent of availability of interatomic potentials. The asymptotic strain gradient elasticity solution for displacement components near the crack tip in materials with cubic lattice was also derived.     

Desorption and ionization mechanisms in desorption atmospheric pressure photoionization

The factors influencing desorption and ionization in newly developed desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS) were studied. Redirecting the DAPPI spray was observed to further improve the versatility of the technique: for dilute samples, parallel spray with increased analyte signal was found to be the best suited, while for more concentrated samples, the orthogonal spray with less risk for contamination is recommended. The suitability of various spray solvents and sampling surface materials was tested for a variety of analytes with different polarities and molecular weights. As in atmospheric pressure photoionization, the analytes formed [M + H](+), [M - H](-), M(+*), M(-*), [M - H + O](-), or [M - 2H + 2O](-) ions depending on the analyte, spray solvent, and ionization mode. In positive ion mode, anisole and toluene as spray solvents promoted the formation of M(+*) ions and were therefore best suited for the analysis of nonpolar compounds (anthracene, benzo[a]pyrene, and tetracyclone). Acetone and hexane were optimal spray solvents for polar compounds (MDMA, testosterone, and verapamil) since they produced intensive [M + H](+) ion peaks of the analytes. In negative ion mode, the type of spray solvent affected the signal intensity, but not the ion composition. M(-*) ions were formed from 1,4-dinitrobenzene, and [M - H + O](-) and [M - 2H + 2O](-) ions from 1,4-naphthoquinone, whereas acidic compounds (naphthoic acid and paracetamol) formed [M - H](-) ions. The tested sampling surfaces included various materials with different thermal conductivities. The materials with low thermal conductivity, i.e., polymers like poly(methyl methacrylate) and poly(tetrafluoroethylene) (Teflon) were found to be the best, since they enable localized heating of the sampling surface, which was found to be essential for efficient analyte desorption. Nevertheless, the sampling surface material did not affect the ionization mechanisms.     

APPLICATION OF CHROMATIC MONITORING AS A PLASMA DIAGNOSTIC TECHNIQUE

This paper describes the application of chromatic monitoring of both laboratory and industrial plasmas. The light emitted from the nitrogen plasma generated in the different plasma sources was measured with an imaging spectrograph. The emission spectra were reduced to data points representing the chromatic coordinates of these spectra. The data compression makes this method attractive for monitoring plasma parameter changes. The aim of this work was to test the possibility of application of chromatic monitoring for plasma processing.     

Effect of enzymatic degradation of chitosan in polyhydroxybutyrate/chitosan/calcium phosphate composites on in vitro osteoblast response

Polyhydroxybutyrate/chitosan/calcium phosphate composites are interesting biomaterials for utilization in regenerative medicine and they may by applied in reconstruction of deeper subchondral defects. Insufficient informations were found in recent papers about the influence of lysozyme degradation of chitosan in calcium phosphate/chitosan based composites on in vitro cytotoxicity and proliferation activity of osteoblasts. The effect of enzymatic chitosan degradation on osteoblasts proliferation was studied on composite films in which the porosity of origin 3D scaffolds was eliminated and the surface texture was modified. The significantly enhanced proliferation activity with faster population growth of osteoblasts were found on enzymatically degraded biopolymer composite films with α-tricalcium phosphate and nanohydroxyapatite. No cytotoxicity of composite films prepared from lysozyme degraded scaffolds containing a large fraction of low molecular weight chitosans (LMWC), was revealed after 10 days of cultivation. Contrary to above in the higher cytotoxicity origin untreated nanohydroxyapatite films and porous composite scaffolds. The results showed that the synergistic effect of surface distribution, morphology of nanohydroxyapatite particles, microtopography and the presence of LMWC due to chitosan degradation in composite films were responsible for compensation of the cytotoxicity of nanohydroxyapatite composite films or porous composite scaffolds.     

Some insights from recent applications of HRA methods in PSA effort and plant operation feedback in Czech Republic

The methods of human reliability analysis (HRA) form an integral part of probabilistic safety assessment. These methods are currently still under development and there is significant lack of data needed for applications. As a consequence, no unique formal approach for solution of many aspects related to plant staff human performance does exist.In this contribution, some examples of fruitful work are given, which reflect the needs and possibilities specific for HRA field. In the first two examples, methodology, course and results of analysis of concrete matters related to pre-accident errors and shutdown control room crew performance are described. The last example is oriented to one potential human performance related data source-observation of control room crew full-scope simulator exercise. Some conclusions of general validity are presented in the final part of the contribution.     

Study of structure and properties of ZnO–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Glasses of the ternary system ZnO–Bi₂O₃–P₂O₅ were prepared and studied in two compositional series 50ZnO–xBi₂O₃–(50 − x)P₂O₅ and (50 − y)ZnO–yBi₂O₃–50P₂O₅. Two distinct glass-forming regions were found in the 50ZnO–xBi₂O₃–(50 − x)P₂O₅ glass series with x = 0–10 and 20–35 mol.% Bi₂O₃. All prepared Bi₂O₃-containing glasses reveal a high chemical durability. Small additions of Bi₂O₃ (∼5 mol.%) improve thermal stability of glasses. All glasses crystallize on heating within the temperature range of 505–583 °C. Structural studies by Raman and ³¹P MAS NMR spectroscopies showed the rapid depolymerisation of phosphate chains within the first region with x = 0–15 and the presence of isolated Q⁰ phosphate units within the second region with x = 20–35. Raman studies showed that bismuth is incorporated in the glass structure in BiO₆ units and their vibrational bands were observed within the spectral region of 350–700 cm⁻¹. The evolution of properties and the spectroscopic data are both in accordance with a network former effect of Bi₂O₃.     

Microchip sonic spray ionization

The first microchip version of sonic spray ionization (SSI) as an atmospheric pressure ionization source for mass spectrometry (MS) is presented. The microchip used for SSI has recently been developed in our laboratory, and it has been used before as an atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) source. Now the ionization is achieved simply by applying high (sonic) speed nebulizer gas, without heat, corona discharge, or high voltage. The microchip SSI was applied to the analysis of tetra-N-butylammonium, verapamil, testosterone, angiotensin I, and ibuprofen. The limits of detection were in the range of 15 nM to 4 microM. The technique was found to be highly dependent on the position of the chip toward the mass spectrometer inlet, and on the gas and the sample solution flow rates. The microchip SSI provided dynamic linearity following a pattern similar to that used with electrospray, good quantitative repeatability (RSD=16%), and long-term signal stability.