Speciation analysis of aluminium and aluminium fluoride complexes by HPIC-UVVIS

The study presents a new analytical method for speciation analysis in fractionation of aluminium fluoride complexes and free Al³⁺ in soil samples. Aluminium speciation was studied in model solutions and soil extract samples by means of high performance ion chromatography (HPIC) with UV-VIS detection using post-column reaction with tiron for the separation and detection of aluminium fluoride complex and Al³⁺ forms during one analysis. The paper presents particular stages of the chromatographic process optimization involving selecting the appropriate eluent strength, type of elution or concentration and quantity of derivatization reagent. HPIC was performed on a bifunctional analytical column Dionex IonPac CS5A. The use of gradient elution and the eluents A: 1 M NH₄Cl and B: water acidified to pH of eluent phase, enabled full separation of fluoride aluminium forms as AlF₂⁺, AlF₃⁰, AlF₄⁻ (first signal), AlF²⁺ (second signal) and form Al³⁺ in a single analytical procedure. The proposed new method HPIC-UVVIS was applied successfully in the quantitative and qualitative analysis of soil samples.     

Yttria-stabilized zirconia films deposited by plasma spraying and sputtering

Thin films of yttria-stabilized zirconia (YSZ) deposited by sputtering and plasma spraying have been analysed as solid electrolyte for oxygen gas sensors and solid oxide fuel cells. Different substrates have been considered in order to provide good adhesion, dense electrolyte films, and mechanical and thermal stability. By optimization of the sputtering parameters, a Pt/YSZ/Pt assembly of 1.5 µm thickness and with an electrical resistance of 500 M at room temperature has been obtained. The plasma-sprayed films (150 µm thickness) have shown oxygen ion conductivity with a reproducible sensitivity on oxygen partial pressure starting at 400 °C and an activation energy of ~1 eV. Lanthanum strontium manganate (350 µm thickness) was sprayed as cathode material.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003     

Geometric H/D isotope effects and cooperativity of the hydrogen bonds in porphycene.

We investigate the primary, secondary, and vicinal hydrogen/deuterium (H/D) isotope effects on the geometry of the two intramolecular hydrogen bonds in porphycene. Multidimensional potential energy surfaces describing the anharmonic motion in the vicinity of the trans isomer are calculated for the different symmetric (HH/DD) and asymmetric (HD) isotopomers. From the solution of the nuclear Schr?dinger equation the ground-state wavefunction is obtained, which is further used to determine the quantum corrections to the classical equilibrium geometries of the hydrogen bonds and thus the geometric isotope effects. In particular, it is found that the hydrogen bonds are cooperative, that is, both expand simultaneously even in the case of an asymmetric isotopic substitution. The theoretical predictions compare favorably with NMR chemical-shift data.     

EPR study of free radicals in γ-irradiated thiazide compounds

The aim of this paper was to identify the type of radicals formed by γ-irradiation in powdered chlorothiazide (CTZ), hydrochlorothiazide (HCTZ), althiazide (ATZ) and trichloromethiazide (TCTZ) on the basis of analysis of their electron paramagnetic resonance spectra with enhanced resolution. In TCTZ, HCTZ and ATZ the radical was formed by abstraction of a hydrogen atom from the carbon atom C-3, and in the case of CTZ by addition of a hydrogen atom to the nitrogen atom N-4. The hyperfine structure is found. The electron densities at nitrogen atom positions in the N-C-N group in HCTZ, ATZ and TCTZ depend on a single 3-position substitution and are in line with their diuretic potency.     

Molecular and crystal structure of bis-quinolizidine immonium salts,II: Δ1(6)-dehydrosparteinium monoperchlorate

₁₍₆₎-Dehydrosparteinium monoperchlorate, [C₁₅H₂₅N₂]⁺·ClO ₄ ^– , is orthorhombicP2₁2₁2₁,a=12.473(2),b=24.292(3),c=10.835(1) Å,V _c =3353.7(9) ų,Z=8,D _x =1.32,D _m =1.32 g cm^–3, (CuK)=20.7 cm^–1. The finalR was 0.097 for 2091 observed counter reflections. A partial disorder of the crystal structure has been observed. The two independent perchlorate anions are orientationally disordered, and the peripheral atoms in the cation skeletons have large temperature factors due both to conformational disorder of ringsA and to disordered orientations of the whole cations alike. In ringsA, atoms C(3) and C(4), trans-annular to the immonium bond, are disordered to a different extent in each of the two independent cations. RingsB,C, andD have sofa (distorted towards half-chair), chair, and chair conformations, respectively. The quinolizidinium and quinolizidine moieties have planar and cis configurations, respectively. The title compound was obtained from ⁵-dehydrosparteine, the product of mercuric acetate dehydrogenation of sparteine at room temperature. From¹³C NMR measurements in²H₂O and in DMSO-²H₆ it is evident that, in solution, the molecular geometry with chair/chair cis-ring fusion within the quinolizidine moiety is present, as was found in the crystalline state by X-ray analysis.     

An In‐Depth Look at the Reactivity of Non‐Redox‐Metal Alkylperoxides

Over the past 150 years, a certain mythology has arisen around the mechanistic pathways of the oxygenation of organometallics with non‐redox‐active metal centers as well as the character of products formed. Notably, there is a widespread perception that the formation of commonly encountered metal alkoxide species results from the auto‐oxidation reaction, in which a parent metal alkyl compound is oxidized by the metal alkylperoxide via oxygen transfer reaction. Now, harnessing a well‐defined zinc ethylperoxide incorporating a β‐diketiminate ligand, the investigated alkylperoxide compounds do not react with the parent metal alkyl complex as well as Et₂Zn to form a zinc alkoxide. Upon treatment of the zinc ethylperoxide with Et₂Zn, a previously unobserved ligand exchange process is favored. Isolation of a zinc hydroxide carboxylate as a product of decomposition of the parent zinc ethylperoxide demonstrates the susceptibility of the latter to O?O bond homolysis.     

An efficient semi‐implicit subgrid method for free‐surface flows on hierarchical grids

We present a new modelling strategy for improving the efficiency of computationally intensive flow problems in environmental free‐surface flows. The approach combines a recently developed semi‐implicit subgrid method with a hierarchical grid solution strategy. The method allows the incorporation of high‐resolution data on subgrid scale to obtain a more accurate and efficient hydrodynamic model. The subgrid method improves the efficiency of the hierarchical grid method by providing better solutions on coarse grids. The method is applicable to both steady and unsteady flows, but we particularly focus on river flows with steady boundary conditions. There, the combined hierarchical grid–subgrid method reduces the computational effort to obtain a steady state with factors up to 43. For unsteady models, the method can be used for efficiently generating accurate initial conditions on high‐resolution grids. Additionally, the method provides automatic insight in grid convergence. We demonstrate the efficiency and applicability of the method using a schematic test for the vortex shedding around a circular cylinder and a real‐world river case study. Copyright © 2015 John Wiley & Sons, Ltd.     

Substituted Benzophenones as Photoinitiators

Substituted benzophenone photoinitiators were synthesized and characterized by spectroscopy methods. Their absorption spectra and kinetics of the polymerization were compared to benzophenone itself. The kinetics of the photopolymerization of 2-ethyl-2-(hydroxymethyl)-1,3-propanediol triacrylate (TMPTA) was studied by measuring the polymerization heat evolution of sample, irradiated with a laser. The influence of photoinitiator concentration and light intensity on the polymerization was also studied.     

Antimicrobial Activity and Barrier Properties against UV Radiation of Alkaline and Enzymatically Treated Linen Woven Fabrics Coated with Inorganic Hybrid Material

One of the directions of development in the textiles industry is the search for new technologies for producing modern multifunctional products. New solutions are sought to obtain materials that will protect humans against the harmful effects of the environment, including such factors as the activity of microorganisms and UV radiation. Products made of natural cellulose fibers are often used. In the case of this type of material, it is very important to perform appropriate pretreatment before subsequent technological processes. This treatment has the aim of removing impurities from the surface of the fibers, which results in the improvement of sorption properties and adhesion, leading directly to the better penetration of dyes and chemical modifiers into the structure of the materials. In this work, linen fabrics were subjected to a new, innovative treatment being a combination of bio-pretreatment using laccase from Cerrena unicolor and modification with CuO-SiO₂ hybrid oxide microparticles by a dip-coating method. To compare the effect of alkaline or enzymatic pretreatment on the microstructure of the linen woven fabrics, SEM analysis was performed. The new textile products obtained after this combined process exhibit very good antimicrobial activity against Candida albicans, significant antibacterial activity against the Gram-negative Escherichia coli and the Gram-positive Staphylococcus aureus, as well as very good UV protection properties (ultraviolet protection factor (UPF) > 40). These innovative materials can be used especially for clothing or outdoor textiles for which resistance to microorganisms is required, as well as to protect people who are exposed to long-term, harmful effects of UV radiation.