Oxidative polymerization of anilinium 5-sulfosalicylate with peroxydisulfate in water

Anilinium 5-sulfosalicylate was prepared and characterized by elemental analysis, and FTIR and NMR spectroscopies. It was polymerized in an aqueous solution using ammonium peroxydisulfate as an oxidant. The precipitated polyaniline 5-sulfosalicylate exhibited high thermal stability and conductivity of 0.13 S cm⁻¹. Its mass-average molar mass and polydispersity index were determined by gel-permeation chromatography as 22,900 g mol⁻¹ and 2.7, respectively. Elemental analysis and FTIR spectroscopy study of polyaniline 5-sulfosalicylate revealed the doping level and the oxidation state between emeraldine and protoemeraldine salt while corresponding studies of the polyaniline base indicate a small extent of the covalent bonding of 5-sulfosalicylate anions to polyaniline chains.     

Annihilation of nematic point defects: Pre-collision and post-collision evolution

The annihilation of the nematic hedgehog and anti-hedgehog within an infinite cylinder of radius R is studied. The semi-microscopic lattice-type model and Brownian molecular dynamics are used. We distinguish among the i) early pre-collision, ii) late pre-collision, iii) early post-collision, and iv) late post-collision stages. In the pre-collision stage our results agree qualitatively with the existing experimental observations and also continuum-type simulations. The core of each defect exhibits a ring-like structure, where the ring axis is set perpendicular to the cylinder symmetry axis. For ξ⁽⁰⁾_d/(2R) > 1 the interaction between defects is negligible, where ξ⁽⁰⁾_d describes the initial separation of defects. Consequently, the defects annihilate within the simulation time window for ξ⁽⁰⁾_d/(2R) < 1. For close enough defects their separation scales as ξ_d (t_c - t)^0.4±0.1, where t_c stands for the collision time. In elastically anisotropic medium the hedgehog is faster than the anti-hedgehog. In the early pre-collision stage the defects can be treated as point-like particles, possessing inherent core structure, that interact via the nematic director field. In the late pre-collision stage the cores reflect the interaction between defects. After the collision a charge-less ring structure is first formed. In the early post-collision stage the ring adopts an essentially untwisted circular structure of the radius ξ_r. In the late post-collision stage we observe two qualitatively different scenarios. For μ = ξ_r/R < μ_c ∼ 0.25 the ring collapses leading to the escaped radial equilibrium structure. For μ > μ_c the chargeless ring triggers the nucleation growth into the planar polar structure with line defects.     

Interactions in clay/electrolyte systems

The sorption of cesium and cobalt on kaolinite and montmorillonite were followed by radiotracer method. The sorption of cesium can be described by a Freundlich isotherm. Cobalt sorption on clays equilibrated in cesium chloride solutions significantly differs for kaolinite and montmorillonite due to their differences in sites available for cation sorption and changes in solution chemistry.Heterogeneous exchange of cesium ions between clay and the surrounding electrolyte was performed in order to obtain information about clay/electrolyte systems equilibration. An interplay of different processes included in the attainment of true chemical equilibria of clay/electrolyte systems are responsible for the change of clay surface properties and total exchange capacity.     

The fragmentation of doubly charged ions of halogenated benzenes

The unimolecular charge separation fragmentations of doubly charged benzene and 18 derivatives containing various numbers of fluorine, chlorine and bromine atoms have been studied. In the majority of cases two distinct kinds of transition state can be characterized, in one of which the ring system remains intact and in the other of which a linear transition state ion is formed. There is evidence for rearrangement of halogens both around the ring and along the linear chain.     

Three‐dimensional networks containing rectangular Sr4 and Ba4 units: Synthesis,structure, bonding,and potential application for Ne gas separation

New porous three‐dimensional metal‐organic frameworks are synthesized that contain infinite chains of Sr_n and Ba_n rectangles. Their structures are elucidated by means of spectroscopic techniques such as nuclear magnetic resonance and Fourier transform infrared, and the respective crystal structures are determined. The electronic structure of basic units of the crystals are computed using density functional theory at the B3LYP/6‐31G(d,p)/def2‐TZVP level, and the bonding and reactivity are analyzed using natural bond orbital analysis, the quantum theory of atoms in molecules, and conceptual density functional theory. The possibilities of noble gas (Ng) storage inside the crystal structures are explored through modeling a Ng atom inside the frozen geometry of the crystal. It was found that a neon atom can fit into a cavity in the Sr and Ba crystal structures whereas other Ngs (He, Ar, Kr) exhibit repulsive interactions with the crystal structure. Ab initio molecular dynamics simulations for up to 500 fs at 77 and 298 K suggest that the structures incorporating a neon atom are kinetically stable. © 2015 Wiley Periodicals, Inc.     

Determination of critical micellar concentrations of cholic acid and its keto derivatives

The critical micellar concentration (CMC) values of keto derivatives of cholic acid (3,12-dihydroxy-7-oxo-5β-cholanoic acid, 3,7-dihydroxy-12-oxo-5β-cholanoic acid, 12-hydroxy-3,7-dioxo-5β-cholanoic acid, 3-hydroxy-7,12-dioxo-5β-cholanoic acid, 3,7,12-triketo-5β-cholanoic acid) and cholic acid itself, were determined. Replacement of hydroxyl groups in cholic acid molecule with keto groups yields the derivatives whose CMC values increase with increase in the number of keto groups introduced. The CMCs of derivatives with the same number of keto groups but at different positions do not differ significantly. The relationship between the number of keto groups in the molecule of cholic acid keto derivatives and CMC value can be described by the following equation: CMC = 43 number of keto groups + 14.667. The effect of NaCl concentration on CMC increases with increase in the number of keto groups.     

Influence of polar dopant on internal configuration of azoxybenzene nematic-in-water droplets

We report the study of optical textures and director configurations within nematic-in-water microdroplets of the liquid-crystalline mixtures based on azoxybenzene and cyanobiphenyl (as a polar dopant). Both pure azoxybenzene and polar dopant materials exhibited bipolar configuration within liquid-crystalline droplets, whereas their mixtures at appropriate concentrations spontaneously formed radial droplets. It was found that increasing of the dopant’s concentration resulted in the forward tangential-homeotropic and reentrant homeotropic-tangential anchoring transitions. We also triggered bipolar-to-radial structural transition by UV irradiation providing trans-cis isomerisation of nematogens. Critical irradiation time needed for radial configuration formation was found to decrease with concentration of polar dopant. Mesoscoping modelling is proposed to explain main experimental results. The presented data are discussed for chemical and biological sensing applications.     

Supercritical Carbon Dioxide Extraction of Four Medicinal Mediterranean Plants: Investigation of Chemical Composition and Antioxidant Activity

With everyday advances in the field of pharmaceuticals, medicinal plants have high priority regarding the introduction of novel synthetic compounds by the usage of environmentally friendly extraction technologies. Herein, a supercritical CO₂ extraction method was implemented in the analysis of four plants (chamomile, St. John’s wort, yarrow, and curry plant) after which the non-targeted analysis of the chemical composition, phenolic content, and antioxidant activity was evaluated. The extraction yield was the highest for the chamomile (5%), while moderate yields were obtained for the other three plants. The chemical composition analyzed by gas chromatography-high-resolution mass spectrometry (GC-HRMS) and liquid chromatography-high-resolution mass spectrometry (LC-HRMS) demonstrated extraction of diverse compounds including terpenes and terpenoids, fatty acids, flavonoids and coumarins, functionalized phytosterols, and polyphenols. Voltammetry of microfilm immobilized on a glassy carbon electrode using square-wave voltammetry (SWV) was applied in the analysis of extracts. It was found that antioxidant activity obtained by SWV correlates well to 1,1-diphenyl-2-picrylhidrazine (DPPH) radical assay (R² = 0.818) and ferric reducing antioxidant power (FRAP) assay (R² = 0.640), but not to the total phenolic content (R² = 0.092). Effective results were obtained in terms of activity showing the potential usage of supercritical CO2 extraction to acquire bioactive compounds of interest.