Mössbauer Study of the Thermal Behaviour of Garnets Used in High-Energy Water Jet Technologies

A high-energy water jet combined with silicate garnets as abrasives has been proven to be a powerful tool for disintegration of hard materials. Thermal heating of the garnets is one way for structure improvement of the abrasive material. Room-temperature Mössbauer spectra of initial powdered almandine samples are characterised by one doublet corresponding to Fe²⁺ in dodecahedral position 24c. Almandine garnet, industrial product Barton HP 80 as reference material in all experiments, has a second doublet corresponding to Fe³⁺ in octahedral position 16a. In room-temperature spectra of heated almandine garnet samples from locality Ktí and Mdnec (heated under temperatures 200–1000°C by 100 degrees for 1 hour in air) a new doublet originating from -Fe₂O₃ nanoparticles appeared. Under a heating temperature of higher than 800°C, the broad sextets of -Fe₂O₃ and -Fe₂O₃ in spectra were discovered. No additional doublets or sextets appeared in room-temperature Mössbauer spectra of reference material of almandine garnet Barton HP 80 heated under each temperature.     

Applications of NMR spectroscopy of chiral association complexes. 6. rotation about the C(sp2)—C(aryl) bond in 2,6-disubstituted pivalophenones

For the investigation of the barrier to rotation about the C(sp²)—C(aryl) bond in non-planar pivalophenones five derivatives were prepared and their ¹H and ¹³C NMR spectra assigned. Methyl and bromine groups in the 3-position have opposite substituent effects on the chemical shifts of the ¹H and ¹³C signals of Me² and Me⁴. The ΔG values were determined from the coalescence temperatures of the signal splittings generated by the addition of optically active shift reagents. The accuracy of this method was estimated by using different signals of 3-bromo-2,4,6-trimethylpivalophenone and by computer simulation of the line shape. A buttressing effect of substituents in the aromatic ring was observed. A change of the twist angle by the substitution of methyl by bromine in the tert-butyl group was suggested in order to explain the changes in ΔG and the chemical shifts.     

Deterministic solution of the kinetic theory model of colloidal suspensions of structureless particles

A direct modeling of colloidal suspensions consists of calculating trajectories of all suspended objects. Due to the large time computing and the large cost involved in such calculations, we consider in this paper another route. Colloidal suspensions are described on a mesoscopic level by a distribution function whose time evolution is governed by a Fokker–Planck-like equation. The difficulty encountered on this route is the high dimensionality of the space in which the distribution function is defined. A novel strategy is used to solve numerically the Fokker–Planck equation circumventing the curse of dimensionality issue. Rheological and morphological predictions of the model that includes both direct and hydrodynamic interactions are presented in different flows.     

How to confirm identified toxicants in effect-directed analysis

Due to the production and use of a multitude of chemicals in modern society, waters, sediments, soils and biota may be contaminated with numerous known and unknown chemicals that may cause adverse effects on ecosystems and human health. Effect-directed analysis (EDA), combining biotesting, fractionation and chemical analysis, helps to identify hazardous compounds in complex environmental mixtures. Confirmation of tentatively identified toxicants will help to avoid artefacts and to establish reliable cause–effect relationships. A tiered approach to confirmation is suggested in the present paper. The first tier focuses on the analytical confirmation of tentatively identified structures. If straightforward confirmation with neat standards for GC–MS or LC–MS is not available, it is suggested that a lines-of-evidence approach is used that combines spectral library information with computer-based structure generation and prediction of retention behaviour in different chromatographic systems using quantitative structure–retention relationships (QSRR). In the second tier, the identified toxicants need to be confirmed as being the cause of the measured effects. Candidate components of toxic fractions may be selected based, for example, on structural alerts. Quantitative effect confirmation is based on joint effect models. Joint effect prediction on the basis of full concentration–response plots and careful selection of the appropriate model are suggested as a means to improve confirmation quality. Confirmation according to the Toxicity Identification Evaluation (TIE) concept of the US EPA and novel tools of hazard identification help to confirm the relevance of identified compounds to populations and communities under realistic exposure conditions. Promising tools include bioavailability-directed extraction and dosing techniques, biomarker approaches and the concept of pollution-induced community tolerance (PICT). Figure Toxicity confirmation in EDA as a tiered approach     

Small camera as a handheld colorimetric tool in the analytical chemistry

Recently, there is an effort to introduce new types of analytical procedures and handheld assays to provide simple and reliable equipment for the field and household analyses. Development of diagnostic tools for self-diagnosis is another challenge in analytical chemistry. Digital cameras are widely available and cheap, hence they could be the sensor platform for construction of analytical and diagnostic methods. In general, good availability of cameras integrated into smartphones can be easily converted into an analytical tool. This review relates to the use of digital camera in analytical chemistry and there are introduced the facts how digital data can be processed and what the limits of digital photography are. Recent papers in this issue and discussion of development in camera based assays is also provided here.     

Capillary electrophoretic study of interactions of metal ions with crown ethers,a sulfated beta-cyclodextrin,and zwitterionic buffers present as additives in the background electrolyte

Stability constants of K, Na, Ca, and Ba with 18-crown-6, K, Na, Li with sulfated beta-cyclodextrin and K, Li, Ca, Mg, Sr, and Ba ions with ([2-hydroxy-1,1-bis(hydroxymethyl) ethyl]-amino)-1-propanesulfonic acid (TAPS) were determined by capillary electrophoresis and computed using a general least squares minimizing program CELET. The results for 18-crown-6 agreed well with those evaluated by graphical methods or reported in the literature. Previously unknown stability constants of sulfated beta-cyclodextrins and TAPS determined for alkali and alkaline earth metals show that sulfated beta-cyclodextrin interacts with monovalent metals allowing to manipulate their effective mobility. It interacts stronger with divalent metal cations. TAPS, as zwitterionic buffer widely used in various analytical, biochemical and other applications, forms complexes with alkali and alkaline earth cations, and although the stability constants are rather low, the equilibria should be taken into account when TAPS is used and metal cations are present in solution at the same time.     

Modelling,optimisation and control of selectivity in the separation of aromatic bases by electrokinetic chromatography using a neutral cyclodextrin as a pseudostationary phase

A simple mathematical model describing the separation of a series of aromatic bases by electrokinetic chromatography using beta-cyclodextrin (beta-CD) as a pseudostationary phase is described. The model takes into account changes in electrolyte pH and the different formation constants between the neutral and charged forms of the analytes with the CD. Constants in the model were obtained within the two-dimensional experimental space defined by pH and [beta-CD] with nonlinear regression using only five experimental points. These constants agreed with expected trends in analyte-CD interactions and predicted much higher formation constants for the neutral analyte-CD complex than for the charged analyte-CD complex. Correlation between predicted and observed mobilities using additional 20 points within the experimental space gave r(2) = 0.995. Optimisation of the pH and [beta-CD] was performed using both the normalised resolution product and minimum resolution product criteria and provided two optimum separations which exhibited different selectivities. Differences between predicted and observed migration times at these optima were less than 2.5 and 5% for the normalised resolution product and the minimum resolution criteria, respectively. In both cases the correct migration order was predicted. The model was also applied successfully to the optimisation of conditions for the separation of a specific mixture of analytes or for conditions under which particular analytes migrated in a desired order.     

Photoinduced phase transitions and helix untwisting in the SmC* phase of a novel cinnamoyl-based liquid crystal

A photoinduced phase transition and helix untwisting in a new liquid crystal forming the SmC* phase were studied in detail. The compound consists of a cinnamoyl photosensitive fragment with C?=?C double bond capable of photoisomerisation and photocycloaddition. It was shown that ultraviolet (UV) irradiation (365 nm) induces an extreme decrease in phase transitions temperatures (SmC*–SmA*, SmA*–N*, N*–I). Vertically aligned samples in the SmC* phase cause selective light reflection in the visible spectral range. The light action results in a noticeable helix untwisting that causes a shift in the selective light reflection peak to the long-wavelength spectral region. The temperature dependence of spontaneous polarisation P _s was measured and it was found that UV irradiation induces a decrease in the values of P _s. Photo-optical phenomena taking place in the liquid crystal are attributed to the formation of photoproducts having low anisometry, which disrupts mesophases.     

Pressurised solvent extraction of nitrated derivatives of polycyclic aromatic hydrocarbons from roadside dust

An analytical method based upon the pressurised solvent extraction and gas chromatography and mass spectrometry (GC-MS) for analysis of nitrated derivatives of polycyclic aromatic hydrocarbons (nitro-PAHs) in roadside dust has been developed. Five nitro-PAHs (1-nitronaphthalene, 1-nitropyrene, 9-nitroanthracene, 2-nitrofluorene, 6-nitrochrysene) were chosen for this study because of their variable physical properties and effect on human health. Experiments with spiked inert matrix were used for the best extraction conditions finding. Different extraction conditions (temperature, pressure, solvents and duration of extraction cycle) were examined. The highest recoveries were observed at the extraction pressure of 14?MPa, temperature of 100°C and two cycles of 5?min extraction time, when dichloromethane was used as an extraction solvent. These conditions were applied to the extraction of nitro-PAHs from roadside dust. After extraction the nitro-PAHs fraction was isolated by the silica gel column chromatography. The GC-MS detector was used for analyses of the extracts. Recoveries of nitro-PAHs after extraction from roadside dust ranged from 60% for 9-nitroanthracene to 108% for 6-nitrochrysene.     

Gas separation properties of ultra-thin films based on fully cyclized polyimides

Fully cyclized polyimides based on octadecyl- or hexadecyl 3,5-diaminobenzoate and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride or 4,4′-oxydiphthalic anhydride were synthesized and deposited by the Langmuir-Schaefer technique onto a poly(1-trimethylsilylprop-1-yne) support. Composite membranes thus prepared show selective gas permeation for N₂, O₂, CO₂, H₂ with permeation rates in the range of 10⁻⁵ to 10⁻⁷ cm³ (STP)/(cm² · s · cmHg).