Dielectric modes in antiferroelectric liquid crystal observed at low temperatures

A broad temperature antiferroelectric binary mixture has been investigated by means of dielectric spectroscopy. The sample was cooled down to –70°C. It was found that the sample was still in antiferroelectric phase. This is the widest antiferroelectric mixture ever seen (～170°) in which three well-separated modes have been detected at room temperature. In addition, the bias field influence on existing modes has been observed. All modes change their strengths with bias field. Results show that the fastest mode, called X mode previously, gradually disappears around –30°C. When the temperature decreases below –40°C, one can indisputably observe additional mode, faster than X mode. This mode (named as Y mode) observed for extra low temperatures is bias independent. It can be the molecular mode, connected with rotation around long molecular axis. The rotation around short molecular axis seems to be blocked in antiferroelectric packing. To calculate parameters of observed modes, Cole–Cole model was used. The parameters of Y mode are discussed in this article.     

Influence of the bias field on dielectric properties of the SmCA* in the vicinity of the SmC*–SmCA* phase transition

In a large class of smectic mixtures prepared at our University, the phase transition between chiral ferroelectric smectic C (SmC*) and chiral antiferroelectric smectic C (SmC_A*) phases can be observed on cooling. Under bias field the temperature of the phase transition SmC*?SmC_A* decreases (ca. 100°C in the investigated mixture). The transition is called: unwound SmC*?twisted SmC_A* phase transition. The Goldstone mode in SmC* phase is reduced by a direct current field while two modes (P_H and P_L) in the SmC_A* phase are amplified. The amplitude of the fast X mode observed in the SmC_A* phase is reduced. The aim of this paper is to show how parameters of the modes in SmC_A* phase (calculated from Cole–Cole model) change with bias voltage—when twisted structure in SmC_A* phase is gradually unwound. The character of the modes observed in SmC_A* is discussed. A new effect is shown: a high value of dielectric loss is detected in the unwound SmC* phase, which is very close to SmC_A*.     

Long-lived emission from Eu3+:PbF2 nanocrystals distributed into sol–gel silica glass

This paper reports an optical investigation of Eu³⁺:PbF₂ nanocrystals distributed into silica glasses fabricated by sol–gel methods. The sample microstructure was investigated using scanning transmission electron microscopy. The β-cubic PbF₂ crystalline phase was identified using X-ray diffraction analysis. The observed emission bands correspond to ⁵D₀ → ⁷F_J (J = 0–4) transitions of Eu³⁺. The spectroscopic parameters for Eu³⁺ ions were determined based on excitation and emission measurements as well as luminescence decay analysis. Emission originating from ⁵D₀ state of Eu³⁺ ions in sample containing PbF₂ nanocrystals is long-lived in comparison to precursor sol–gel silica glasses.     

CaZrO3-based powders suitable for manufacturing electrochemical oxygen probes

Calcium zirconate powders doped with a small amount of CaO were synthesised using the Pechini method. X-ray analysis revealed that solid solution was formed in the concentration up to 51.5% mol CaO. For synthesis of stoichiometric CaZrO₃, the highest temperature was required (1150°C), but introduction of excess CaO from 50.5 to 51.5% mol enabled us to lower the synthesis temperature to 800°C. The sintering behaviour of such samples under non-isothermal conditions was studied by dilatometric methods. Deviations were found in stoichiometry; by increasing the CaO concentration in CaZrO₃ sinterability improved in comparison to CaZrO₃ with stoichiometric composition. The presence of CaO as second phase caused deterioration of the sinterability of the CaZrO₃-based samples. Pellets sintered at 1500°C for 2 h reached 96–98% of theoretical density. SEM and TEM observations were used to characterise the microstructure of the prepared samples. The electrical properties of CaZrO₃-based samples were investigated by the AC-impedance spectroscopy method. It was found that introduction of excess CaO into the CaZrO₃ structure caused an increase in ionic conductivity up to the solubility limit. The possibility of using CaZrO₃-based samples for constructing prototype electrochemical oxygen probes to determine activity of oxygen dissolved in molten copper is also demonstrated.      

Path-wise versus kinetic modeling for equilibrating non-Langevin jump-type processes

We discuss two independent methods of solution of a master equation whose biased jump transition rates account for long jumps of Lévy-stable type and admit a Boltzmannian (thermal) equilibrium to arise in the large time asymptotics of a probability density function ρ(x, t). Our main goal is to demonstrate a compatibility of a direct solution method (an explicit, albeit numerically assisted, integration of the master equation) with an indirect pathwise procedure, recently proposed in [Physica A 392, 3485, (2013)] as a valid tool for a dynamical analysis of non-Langevin jump-type processes. The path-wise method heavily relies on an accumulation of large sample path data, that are generated by means of a properly tailored Gillespie’s algorithm. Their statistical analysis in turn allows to infer the dynamics of ρ(x, t). However, no consistency check has been completed so far to demonstrate that both methods are fully compatible and indeed provide a solution of the same dynamical problem. Presently we remove this gap, with a focus on potential deficiencies (various cutoffs, including those upon the jump size) of approximations involved in simulation routines and solutions protocols.     

A new ion imprinted polymer based on Ru(III)-thiobarbituric acid complex for solid phase extraction of ruthenium(III) prior to its determination by ETAAS

A new ruthenium ion imprinted polymer was prepared from the Ru(III) 2-thiobarbituric acid complex (the template), methacrylic acid or acrylamide (the functional monomers), and ethylene glycol dimethacrylate (the cross-linking agent) using 2,2′-azobisisobutyronitrile as the radical initiator. The ion imprinted polymer was characterized and used as a selective sorbent for the solid phase extraction of Ru(III) ions. The effects of type of functional monomer, sample volume, solution pH and flow rate on the extraction efficiency were studied in the dynamic mode. Ru(III) ion was quantitatively retained on the sorbents in the pH range from 3.5 to 10, and can be eluted with 4 mol L^?1 aqueous ammonia. The affinity of Ru(III) for the ion imprinted polymer based on the acrylamide monomer is weaker than that for the polymer based on the methacrylic acid monomer, which therefore was used in interference studies and in analytical applications. Following extraction of Ru(III) ions with the imprint and their subsequent elution from the polymer with aqueous ammonia, Ru(III) was detected by electrothermal atomic absorption spectrometry with a detection limit of 0.21 ng mL^?1. The method was successfully applied to the determination of trace amounts of Ru(III) in water, waste, road dust and platinum ore (CRM SARM 76) with a reproducibility (expressed as RSD) below 6.4 %.

Effects of spice extracts on lipid fraction oxidative stability of cookies investigated by DSC

The addition of natural antioxidants to the bakery products containing fats can extend their shelf life, and it may be more attractive to consumers. In this research, the antioxidant effect of spice extracts and synthetic antioxidant on oxidative stability of fat extracted from cookies was evaluated by differential scanning calorimetry (DSC). The results revealed that addition of spice extracts to the cookies in comparison to cookies without additives reduced the oxidation as evidenced by higher the onset oxidation temperature (t _ON) of antioxidant-treated samples. Using the Ozawa–Flynn–Wall method, the activation energies (E _a/kJ mol^?1) and pre-exponential factors (Z/min^?1) and then induction times (τ/min) were calculated and also used for evaluation of antioxidants efficiency. After baking, cookies were also subjected to sensory studies and to instrumental measurements of colour changes. Among the samples studied, cookies with 0.02 % of rosemary or 0.2 % thyme extracts showed good sensorial acceptability. Cookies fortified with spice extracts also characterised greater lightness compared to the control sample.     

Co(II)-promoted transformation of diethyl(quinolin-2-ylmethyl)phosphonate to quinoline-2-carboxylate (2-qca): Synthetic,structural and magnetic studies of [Co(2-qca)2(EtOH)2]

The interaction of the diethyl(quinolin-2-ylmethyl)phosphonate (2-qmpe) ligand with CoCl₂ · 2H₂O unexpectedly leads to the formation of a compound with the formula [Co(2-qca)₂(EtOH)₂] (2-qca = quinoline-2-carboxylate). This compound is a product of the oxidative cleavage of the C–P bond in 2-qmpe and the formation of the 2-qca ligand. The title compound was characterized by infrared, ligand field, EPR spectroscopy and low temperature magnetic (1.8–300 K) studies. Particularly, the crystal and molecular structures were determined by the X-ray diffraction. The CoN₂O₄ chromophore shows an elongated octahedron geometry, resulting from the two didentate N,O-bonded chelate ligands and two ethanol molecules – quinolil nitrogen atoms are located in axial positions and oxygen atoms are positioned in the basal plane. The crystal packing is due to hydrogen bonds and π–π stacking interactions, which give rise to a three-dimensional (3D) polymeric network. The magnetic properties reflect the molecular character of the compound, with a very weak magnetic exchange interaction. The moments are enhanced due to an important orbital contribution via spin–orbit coupling.     

Electrochemical formation and properties of two-component films of transition metal complexes and C60 or C70

The electrochemically active polymers have been formed during electro-reduction carried out in solution containing fullerenes, C₆₀ or C₇₀, and transition metal complexes of Pd(II), Pt(II), Rh(III), and Ir(I). In these films, fullerene moieties are covalently bounded to transition metal atoms (Pd and Pt) or their complexes (Rh and Ir) to form a polymeric network. All films exhibit electrochemical activity at negative potentials due to the fullerene cages reduction process. For all studied metal complexes, yields of formation of films containing C₇₀ are higher than yields of electrodeposition of their C₆₀ analogs. C₇₀ /M films also exhibit higher porosity in comparison to C₆₀/M layers. The differences in film morphology and efficiency of polymer formation are responsible for differences in electrochemical responses of these films in acetonitrile containing supporting electrolyte only. C₇₀/M films shows more reversible voltammeric behavior in negative potential range. They also show higher potential range of electrochemical stability. Processes of film formation and electrochemical properties of polymers depend on the transition metal ions or atoms bonding fullerene cages into polymeric network. The highest efficiency of polymerization was observed for fullerene/Pd and fullerene/Rh films. In the case of fullerene/Pd films, the charge transfer processes related to the fullerene moieties reduction in negative potential range exhibit the best reversibility among all of the studied systems. Capacitance performances of C₆₀/Pd and C₇₀/Pd films deposited on the porous Au/quartz electrode were also compared. Capacitance properties of both films are significantly affected by the conditions of electropolymerization. Only a fraction of the film having a direct contact with solution contributes to pseudocapacitance. Capacitance properties of these films also depend on the size of cations of supporting electrolyte. The C₇₀/Pd film exhibits much better capacitance performance comparison to C₆₀/Pd polymer.     

The Hydrogen–Deuterium Exchange at α-Carbon Atom in <Emphasis Type="BoldItalic">N,N,N</Emphasis>-Trialkylglycine Residue: ESI-MS Studies

Derivatization of peptides as quaternary ammonium salts (QAS) is a known method for sensitive detection by electrospray ionization tandem mass spectrometry. Hydrogens at α-carbon atom in N,N,N-trialkylglycine residue can be easily exchanged by deuterons. The exchange reaction is base-catalyzed and is dramatically slow at lower pH. Introduced deuterons are stable in acidic aqueous solution and are not back-exchanged during LC-MS analysis. Increased ionization efficiency, provided by the fixed positive charge on QAS group, as well as the deuterium labeling, enables the analysis of trace amounts of peptides.