Permeation of binary gas mixture through glassy polymer membranes with concentration-dependent diffusivities

An analytical solution has been obtained for the modified dual-mode mobility model for a single gas proposed by Zhou and Stern and extended to a binary gas mixture to describe the pressure dependence of mean permeability coefficients for CO₂ and CH₄ mixtures in homogeneous cellulose triacetate membranes. The permeabilities calculated from the model fitted the corresponding experimental results quite well. Permeation experiments for equimolar CO₂ and CH₄ mixture in a homogeneous membrane of methyl methacrylate and n-sbutyl acrylate copolymer were performed along with sorption experiments for pure CO₂ and CH₄ to test the applicability of the model. The experimental permeabilities were close to those calculated from the model.     

Control and coupling of spiral waves in excitable media

We report the complex dynamics of spiral waves observed in the ferroin-catalyzed BZ reaction. The reaction is run in an open unstirred reactor (CFUR) with the catalyst immobilized on a polysulfone membrane. The catalyst-loaded membrane is placed between two well stirred compartments which are fed with solutions of sulfuric acid/malonic acid/bromide and sulfuric acid/bromate, respectively. An electrical field perpendicular to the membrane can be applied via Pt-ring electrodes or, alternatively, via transparent electrodes made of ITO-coated glass. In the field-free case relatively simple target and spiral patterns are observed in the membrane. If an alternating electrical field is applied the spiral core drifts through the membrane. The actual trajectory of the spiral tip depends on the amplitude and frequency of the applied electrical field. If the perturbation parameters are chosen properly the wave fronts break up and new spiral cores emerge under the influence of the alternating field. Complex spatio-temporal patterns may be induced which are reminiscent of "spiral-chaos". After switching off the perturbation the system returns to its previous, "simple" behaviour. Our experimental observations are confirmed by model calculations based on the Barkley model of spiral waves. The technique of using modulated excitability to control the dynamics of spiral waves is further extended to the coupling of two spirals in two CFURs. We present numerical simulations based on two identical excitable reaction-diffusion (RD) systems which are mutually coupled. The coupling is based on the observation of an arbitrarily chosen point inside each of the RD systems: If a chemical wave passes the point of optical observation in system 1 an electric field is applied to system 2 and vice versa. Thus, a local observation made in one system is transformed in a global perturbation of the second CFUR. We report the observation of CFUR states where the two spiral waves are spatially and temporally coupled to each other.     

Pattern formation in thin liquid films with charged surfactants

The dynamic evolution of positively charged surfactants at the interface of a thin film resting atop a negatively charged base is investigated. The lubrication approximation is used to develop coupled equations governing the dynamic evolution of such a system in the presence of charge effects coupled with van der Waals forces. The equations are investigated numerically and analytically, and, for certain parameter ranges, pattern formation is observed reminiscent of that accompanying thermocapillary-driven thin films. Spatial nonuniformities in the charge of the underlying substrate are also studied as a possible tool for film rupture wavelength selection.     

Precipitate pattern formation in fluctuating media

Simulation of the Liesegang pattern formation in low concentration gradient is presented using concentration perturbation in a deterministic model. The precipitation process is based on ion-product supersaturation theory (Ostwald's model). In the classical experiments with high initial concentration gradients, appearance time and locations of the band formation are well reproducible. Decreasing initial concentration gradients results in a more stochastic pattern structure; this means that the reproducibility of the experiments becomes worse. The presented model and the results of the simulations exhibit the same trend, which were demonstrated and investigated experimentally by Kai et al.     

Pattern formation in draining thin film suspensions

We demonstrate the emergence of complexity from remarkably simple and ubiquitous systems: draining thin-film suspensions exhibiting a striking transition between two classes of self-organizing patterns. Vertical channels form when attractive forces lead to transient gelation, while horizontal bands result from granular mixtures. We propose an explanation whereby the generic physical mechanisms require only the existence of viscous and excluded-volume couplings among the particles, solvent, and substrate. System-specific, small inhomogeneities trigger large-scale pattern formation, through collective dynamics, where jamming plays a crucial role. Our results shed light on emergent complexity in bio- and geophysical processes and have implications for coatings and food industries.     

Pattern formation in the iodate-sulfite-thiosulfate reaction-diffusion system

Sodium polyacrylate-induced pH pattern formation and starch-induced iodine pattern formation were investigated in the iodate-sulfite-thiosulfate (IST) reaction in a one-side fed disc gel reactor (OSFR). As binding agents of the autocatalyst of hydrogen ions or iodide ions, different content of sodium polyacrylate or starch has induced various types of pattern formation. We observed pH pulses, striped patterns, mixed spots and stripes, and hexagonal spots upon increasing the content of sodium polyacrylate and observed iodine pulses, branched patterns, and labyrinthine patterns upon increasing the starch content in the system. Coexistence of a pH front and an iodine front was also studied in a batch IST reaction-diffusion system. Both pH and iodine front instabilities were observed in the presence of sodium polyacrylate, i.e., cellular fronts and transient Turing structures resulting from the decrease in diffusion coefficients of activators. The mechanism of multiple feedback may explain the different patterns in the IST reaction-diffusion system.     

Pattern formation in phase separating binary mixtures

We experimentally investigate the interplay of thermodynamics with hydrodynamics during phase separation of (quasi-) binary mixtures. Well defined patterns emerge while slowly crossing the cloud point curve. Depending on the material parameters of the experimental system, two distinct scenarios are observed. In quasi-binary mixtures of methanol-hexane patterns appear before macroscopic phase separation sets in. In course of time the patterns turn faint while the overall turbidity of the sample increases until the mixtures become completely turbid. We attribute this pattern formation to a latent heat induced instability resembling a Rayleigh-Bénard instability. This is confirmed by calorimetric data and an estimate of its Rayleigh number. Mixtures of C(4)E(1)-water doped with decane phase separate under heating. After passing the cloud point curve these mixtures first become homogenously turbid. While clearing up, pattern formation is observed. We attribute this type of pattern formation to an interfacial tension induced Bénard-Marangoni instability. The occurrence of the two scenarios is supported by the relevant dimensionless numbers.     

Pattern formation in the Belousov-Zhabotinsky-PAMAM dendrimer system

The Belousov-Zhabotinsky reaction was studied under the influence of nanometric confinements induced by a complex polymer, the PAMAM-G4 dendrimers. They are well-defined in both molecular weight and architecture and are capable of molecular inclusion, making "unimolecular active micelles". The effect of such nanocompartments in the BZ reaction is analyzed by changing both the excitability and the concentration of the dendrimer, obtaining a wide range of behaviours, ranging from stationary Turing-like patterns to time dependent structures, such as jumping waves or packet waves.     

Photosensitization with alpha-terthienyl: the formation of superoxide ion in aqueous media

It is well known that alpha-terthienyl generates singlet oxygen in organic solvents with high quantum yields. In an aqueous medium, the production of superoxide radical-anion is readily detected by comparing the reduction of ferricytochrome c or nitro blue tetrazolium in the presence and in the absence of superoxide dismutase. Electron transfer reactions from the electronically excited sensitizer are also detected in an argon atmosphere.     

Stable complex formation with boric acid in pyrolysis of levoglucosan in acidic media

The influence of boric acid or phenylboronic acid on thermal conversion of levoglucosan in acidic sulfolane was studied. Although levoglucosan was converted to levoglucosenone, furfural and 5-hydroxymethyl furfural (total yield: 40 mol%) at 200 °C in sulfolane containing 0.1 wt% H₂SO₄, addition of boric acid enormously lowered the yields of these, and instead caused the formation of a stable complex in more than 70 mol% yield. Thus, boric acid substantially suppressed the acid-catalyzed dehydration and formation of furfurals from levoglucosan through complex formation. From the ¹H NMR spectrum, the chemical structure of this complex was confirmed as -d-glucofuranose cyclic 1,2:3,5-bisborate, which was readily hydrolyzed quantitatively to glucose by the addition of water. Phenylboronic acid also exhibited similar influences.     

Pattern formation and fluctuation-induced transitions in protein crystallization

A kinetic model of protein crystallization accounting for the nucleation stage, the growth and competition of solid particles and the formation of macroscopic patterns is developed. Different versions are considered corresponding successively, to a continuous one-dimensional crystallization reactor, a coarse grained two-box model and a model describing the evolution of the space averaged values of fluid and solid material. The analysis brings out the high multiplicity of the patterns. It provides information on their stability as well as on the kinetics of transitions between different states under the influence of the fluctuations.     

Pattern formation during electrodeposition of alloys

The increase in the content of the alloying element in electrodeposited alloys reflects in the changes of their phase composition, when the saturation limit of the lattice of the basic metal is reached. At higher percentages, the excess amount of the alloying element forms one or more new, richer in this element phases. The coatings become multi-phase, heterogeneous and their physical–mechanical properties change. Sometimes an ordered distribution of the different phases of the heterogeneous alloy coating could be observed. Examples of self-organization phenomena during electrodeposition of different alloy systems, such as Ag-Sb, Ag-Bi, Ag-In, Ag-Sn, Ag-Cd, Cu-Sb and In-Co, resulting in pattern formation and formation of spatio-temporal structures on the surface of the obtained coatings are presented and compared. Instabilities resulting in potential or current oscillations are registered in most of the investigated systems. The phase composition of the alloy coatings and especially of the observed pattern is determined and some similarities in the structure of the phases forming the pattern are registered. The pattern formation is registered on the cathode not only in cyanide silver alloys electrolytes, but also during deposition of other alloy systems in acidic electrolytes like Cu-Sb and In-Co. The effect of the natural convection in non-agitated electrolytes on the pattern formation is discussed. The possibility of formation of periodic structured coatings without applying external electrical pulses which could result in appropriate modification of some properties of the electrodeposited alloys is demonstrated. The hypothesis that similar pattern formation could be observed in agitated electrolytes at different hydrodynamic and electrolysis conditions, when the same percentage or the same phase composition of the alloy is reached was examined for Ag-Cd, In-Co and Ag-Sb alloys in jet-plating experiments.     

Ligand-free CuCl-catalyzed C-N bond formation in aqueous media

CuCl-catalyzed N-arylation of alkyl amines and N-heterocycles with substituted aryl iodides and bromides can be carried out in 40% ⁿBu₄N⁺OH⁻ aqueous solution without any ligands.     

Pattern formation and morphology evolution in Langmuir monolayers

We present a study of how patterns formed by Langmuir monolayer domains of a stable phase, usually solid or liquid condensed, propagate into a metastable one, usually liquid expanded. During this propagation, the interface between the two phases moves as the metastable phase is transformed into the more stable one. The interface becomes unstable and forms patterns as a result of the competition between a chemical potential gradient that destabilizes the interface on one hand and line tension that stabilizes the interface on the other. During domain growth, we found a morphology transition from tip splitting to side branching; doublons were also found. These morphological features were observed with Brewster angle microscopy in three different monolayers at the water/air interface: dioctadecylamine, ethyl palmitate, and ethyl stearate. In addition, we observed the onset of the instability in round domains when an abrupt lateral pressure jump is made on the monolayer. Frequency histograms of unstable wavelengths are consistent with the linear-instability dispersion relation of classical free-boundary models. For the case of dendritic morphologies, we measured the radius of the dendrite tip as a function of the dendrite length as well as the spacing of the side branches along a dendrite. Finally, a possible explanation of why Langmuir monolayers present this kind of nonequilibrium growth patterns is presented. In the steady state, the growth behavior is determined by Laplace's equation in the particle density with specific boundary conditions. These equations are equivalent to those used in the theory of morphology diagrams for two-dimensional diffusional growth, where morphological transitions of the kind observed here have been predicted.     

Radical formation during phenol oxidation in aqueous media

Kinetics of oxygen consumption, reaction product formation, and chemiluminescence during polyphenol oxidation by molecular oxygen in alkaline aqueous media with additions of l ‐ascorbic acid (AscH₂) and homocysteine (HCys) has been investigated. In these processes, AscH₂ and HCys have been shown to act as typical radical‐reaction inhibitors that can be used for determinations of the radical formation rates. The rates of radical formation during oxidation of hydroquinone (p‐QH₂), chlorohydroquinone (Cl‐QH₂), 2,5‐dichlorohydroquinone (2,5Cl‐QH₂), catechol (PK), 4‐methylcatechol (4CH₃‐PK), pyrogallol (PG), gallic acid (GK) have been estimated. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 414–422, 2012     

Peptide-directed microstructure formation of polymers in organic media

Synthesis and peptide-guided self-assembly of an organo-soluble peptide-polymer conjugate, comprising a sequence-defined polypeptide and a poly(n-butyl acrylate), are described. The amino acid sequence of the peptide encodes a high tendency to adopt an antiparallel beta-sheet motif, and thus programs the formation of tapelike microstructures. Easy synthesis and controllable self-assembly is ensured by the incorporation of structure breaking switch defects into the peptide segment. This suppresses temporarily the aggregation tendency of the conjugate as shown by circular dichroism, infrared spectroscopy (FT-IR), and atomic force microscopy (AFM). A pH-controlled rearrangement in the switch segments restores the native peptide backbone, triggering the self-assembly process and leading to the formation of densely twisted tapelike microstructures as could be observed by AFM and transmission electron microscopy. The resulting helical superstructures, when deposited on a substrate, are 2.9 nm high, 10 nm wide, and up to 2.3 mum long. The helical pitch is about 37 nm, and the pitch angle is 48 degrees . The helical superstructures undergo defined entanglement to form superhelices, leading to the formation of soft, continuous organo-gels. A twisted two-dimensional core-shell tape is proposed as a structure model, in which the peptide segments form an antiparallel beta-sheet with a polymer shell.     

Soliton‐like regimes,echo and concave spiral waves in mathematical models of biological excitable media

On the basis of numerical simulations with partial reaction‐diffusion equations describing the dynamics of electrical processes in biological excitable tissues, such as a nerve axons and cardiac Purkinje fibers, we have revealed unusual – soliton‐like – regimes of interaction of propagating nonlinear excitation waves: reflection of the colliding waves instead of their annihilation. The specific nature of wave dynamics due to the reflection effects in two‐dimensional excitable media is considered.     

Helix formation in synthetic polymers by hydrogen bonding with native saccharides in protic media

Water-soluble poly(m-ethynylpyridine)s were designed to realize saccharide recognition in protic media. UV/Vis, 1H NMR, and fluorescence measurements revealed that the polymer forms a helical higher order structure by solvophobic interactions between the ethynylpyridine units in the protic medium. The resulting pore in the helix behaves like a binding pocket in proteins, by taking advantage of inwardly directed hydrogen-bonding functional groups of the polymers. Molecular recognition of native saccharides by the polymers was investigated by circular dichroism (CD). The chirality of the saccharide was transferred to the helical sense of the polymers, accompanied by the appearance of induced CDs (ICDs) in the absorptive region of the polymers. In MeOH/water (10/1), mannose and allose showed intense ICDs, and the apparent association constant between the polymer and D-mannose was 14 M(-1).