Strain coupling and scaling invariants in search for effective critical parameters of uniaxial ferroelectrics

A scaling equation of state giving a realistic ratio of Curie–Weiss constants and accounting for coupling of the order parameter with a strain (secondary order parameter) is used to describe the temperature dependence of the electric susceptibility in an external biasing field applied in case of uniaxial ferroelectrics. Explicit expressions for the resulting scaling invariants are given. The power laws for the temperature and field dependence of the maxima and of the inflection points of the susceptibility curves are found. The theory is exemplified by the effective critical behaviour of iono-molecular crystals (CH₃NH₃)₅Bi₂Cl₁₁ (MAPCB) and (CH₃NH₃)₅Bi₂Br₁₁ (MAPBB).     

Investigation of Pd content in C–Pd films for hydrogen sensor applications

Nanocomposite carbonaceous-palladium (Nc-C-Pd) films were synthesized by physical vapor deposition method (PVD). Scanning electron microscopy studies showed that they were composed of carbonaceous matrix containing Pd nanograins. Nc-C-Pd films were also characterized by thermogravimetric analysis, X-ray powder diffraction, and Fourier transform infrared (FTIR) spectral analysis. The content of Pd in films synthesized at different PVD conditions was determined based on TG measurements. Technological parameters of PVD process affected C/Pd ratio. FTIR spectra exhibited characteristic absorption bands for the precursors of carbonaceous-palladium samples (fullerene C₆₀ and palladium acetate). The influence of hydrogen on electrical properties of the films was tested by measuring their resistance in the presence of hydrogen (1% H₂/N₂).     

Solid state NMR spectroscopy as a precise tool for assigning the tautomeric form and proton position in the intramolecular bridges of o-hydroxy Schiff bases

Two analogous Schiff bases, (S,E)-2-((1-hydroxy-3-methyl-1,1-diphenylbutan-2-ylimino)methyl)phenol (1) and (S,Z)-2-hydroxy-6-((1-hydroxy-3-methyl-1,1-diphenylbutan-2-ylamino)methylene)cyclohexa-2,4-dienone (2), exist in the solid state as phenol-imine and keto-amine tautomers, respectively. Their crystal structures were solved using the X-ray diffraction method. Sample 1 forms orthorhombic crystals of space group P2(1)2(1)2(1), while 2 forms monoclinic crystals of space group P2(1). In each sample, one molecule is in the asymmetric unit of the crystal structure. One-dimensional and two-dimensional solid state NMR techniques were used for structure assignment and for inspection of the (13)C and (15)N δ(ii) of the chemical shift tensor (CST) values. NMR study indicates that the span (Ω = δ(11)-δ(33)) and the skew (κ = 3(δ(22)-δ(iso)/Ω) are extremely sensitive to change in the tautomeric form of the Schiff bases. Theoretical calculations of NMR shielding parameters for 1 and 2 and a model compound with reduced aliphatic residue were performed using the GIAO method with B3LYP functional and 6-311++g(d,p) basis sets. From comparative analysis of the experimental and theoretical parameters, it was concluded that the position of hydrogen in the intramolecular bridge has tremendous influence on (13)C and (15)N CST parameters. Inspection of Ω and κ parameters allowed for the establishment of the nature of the hydrogen bonding and the assignment of the equilibrium proton position in the intramolecular bridges in the solid state.     

Modifying the thermosensitivity of copolymers of sodium styrene sulfonate and<Emphasis Type="Italic"> N</Emphasis>-isopropylacrylamide with dodecyltrimethylammonium chloride

The interactions between copolymers of sodium styrene sulfonate (SSS) and N-isopropylacrylamide (NIPAM), anionic polyelectrolytes, and dodecyltrimethylammonium chloride (DTAC), a cationic surfactant, were studied in aqueous solutions of various ionic strengths. The copolymers were found to be thermoresponsive, showing a lower critical solution temperature (LCST). The influence of the polymer composition, the surfactant concentration, and the ionic strength on the LCST was studied. The surfactant was found to interact strongly with the polymer, forming mixed polymer-surfactant micelles. The critical aggregation concentration (cac) of the polymer-surfactant system was found from fluorescence spectroscopy using pyrene as a fluorescent probe. A strong dependence of the anionic polyelectrolyte-cationic surfactant interactions on the structure of the ionic comonomer was observed.     

BMD-TLC — the Useful Technique for Quantitative Analysis of Chelidonine,Chelerithrine and Berberine in Herbal Drugs

JPC – Journal of Planar Chromatography – Modern TLC - Three step bivariant multiple development thin-layer chromatography (BMD-TLC) technique was used in the quantitative analysis of...     

Rapid access to pyrido[1,2,5]triazepin-4-ones through intramolecular nucleophilic aromatic substitution

Several 3-substituted pyrido[1,2,5]triazepin-4-ones and their benzo counterparts have been prepared in three steps from commercial starting materials. The key step involves S_NAr-type intramolecular nucleophilic aromatic substitution of the appropriate hydrazone substrates.     

Software package SIMPRE—Revisited

This article elucidates the pitfalls identified in the software package SIMPRE recently developed by Baldoví et al. (J. Comput. Chem. 2013, 34, 1961) for modeling the spectroscopic and magnetic properties of single ion magnets as well as single‐molecule magnets. Analysis of the methodology used therein reveals that the crystal field parameters (CFPs), expressed nominally in the Stevens formalism, exhibit features characteristic for the CFPs expressed in the Wybourne notation. The resemblance of the two types of CFPs introduces a serious confusion that may lead to wrong comparisons of the CFPs taken from various sources. To clarify this confusion, the properties of the CFPs ( , ) associated with the Stevens operators ( X = S , J , or L ), which belong to the class of the tesseral‐tensor operators, are contrasted with those of the CFPs B_kq associated with the Wybourne operators , which belong to the class of the spherical‐tensor operators. Importantly, the confused properties of Stevens and Wybourne operators may bear on reliability of SIMPRE calculations. To consider this question independent calculations are carried out using the complete approach and compared with those of the restricted approach utilized earlier. It appears that the numerical results of the package SIMPRE are formally acceptable, however, the meaning of the CFPs must be properly reformulated. Several other conceptual problems arising from misinterpretations of the crucial notions and the CFP notations identified therein are also discussed and clarified. © 2014 Wiley Periodicals, Inc.     

Coumarin synthesis on π-acidic surfaces

Catalysis with anion–π interactions is emerging as an important topic in supramolecular chemistry. Among the reactions explored so far on π-acidic surfaces, coumarin synthesis stands out as a cascade process with several coupled anionic transition states. Increasing π-acidity has been shown in a different context to increase transition-state stabilisation and thus catalytic activity. In this report, we explore the possible use of macrocycles to accelerate coumarin synthesis between two π-acidic surfaces. To our disappointment, we found that compared to monomeric π-acids, coumarin synthesis within divalent macrocycles is clearly slower. Hindered access to an overly confined active site within the macrocycles could possibly account for this loss in activity, but several other explanations are certainly possible. However, operational coumarin synthesis on monomeric π-acidic surfaces is shown to tolerate structural modifications. Best results are obtained with structures that aim for proximity without obstructing transition-state stabilisation on the π-acidic surface.     

Photosensitized Damage Inflicted on Plasma Membranes of Live Cells by An Extracellular Generator of Singlet Oxygen—A Linear Dependence of A Lethal Dose on Light Intensity

We describe a study of the influence of a dose rate, i.e. light intensity or photon flux, on the efficiency of induction of a loss of integrity of plasma membranes of live cells in culture. The influence of a photon flux on the size of the light dose, which was capable of causing lethal effects, was measured in an experimental system where singlet oxygen was generated exclusively outside of live cells by ruthenium(II) phenantroline complex. Instantaneous, sensitive detection of a loss of integrity of a plasma membrane was achieved by fluorescence confocal imaging of the entry of this complex into a cell interior. We demonstrate that the size of the lethal dose of light is directly proportional to the intensity of the exciting light. Thus, the probability of a photon of the exciting light inflicting photosensitized damage on plasma membranes diminishes with increasing density of the incident photons.     

Chemical Kinetics of Methane Pyrolysis in Microwave Plasma at Atmospheric Pressure

Results of chemical kinetics modeling in methane subjected to the microwave plasma at atmospheric pressure are presented in this paper. The reaction mechanism is based on the methane oxidation model without reactions involving nitrogen and oxygen. For the numerical calculations 0D and 1D models were created. 0D model uses Calorimetric Bomb Reactor whereas 1D model is constructed either as Plug Flow Reactor or as a chain of Plug Flow Reactor and Calorimetric Bomb Reactor. Both models explain experimental results and show the most important reactions responsible for the methane conversion and production of H₂, C₂H₂, C₂H₄ and C₂H₆ detected in the experiment. Main conclusion is that the chemical reactions in our experiment proceed by a thermal process and the products can be defined by considering thermodynamic equilibrium. Temperature characterizing the methane pyrolysis is 1,500–2,000 K, but plasma temperature is in the range of 4,000–5,700 K, which means that methane pyrolysis process is occurring outside the plasma region in the swirl gas flowing around the plasma.