Wave-pinned filaments of scroll waves

Scroll waves are three-dimensional excitation patterns that rotate around one-dimensional space curves. Typically these filaments are closed loops or end at the system boundary. However, in excitable media with anomalous dispersion, filaments can be pinned to the wake of traveling wave pulses. This pinning is studied in experiments with the 1,4-cyclohexanedione Belousov-Zhabotinsky reaction and a three-variable reaction-diffusion model. We show that wave-pinned filaments are related to the coexistence of rotating and translating wave defects in two dimensions. Filament pinning causes a continuous expansion of the total filament length. It can be ended by annihilating the pinning pulse in a frontal wave collision. Following such an annihilation, the filament connects itself to the system boundary. Its postannihilation shape that is initially the exposed rim of the scroll wave unwinds continuously over numerous rotation periods.     

Theoretical study of pattern formation during the catalytic oxidation of CO on Pt{100} at low pressures

Theoretical studies have thus far been unable to model pattern formation during the reaction in this system on physically feasible length and time scales. In this paper, we derive a computational reaction-diffusion model for this system in which most of the input parameters have been determined experimentally. We model the surface on a mesoscopic scale intermediate between the microscopic size of CO islands and the macroscopic length scale of pattern formation. In agreement with experimental investigations [M. Eiswirth et al., Z. Phys. Chem., Neue Folge 144, 59 (1985)], the results from our model divide the CO and O(2) partial pressure parameter space into three regions defined by the level of CO coverage or the presence of sustained oscillations. We see CO fronts moving into oxygen-covered regions, with the 1 x 1 to hex phase change occurring at the leading edge. There are also traveling waves consisting of successive oxygen and CO fronts that move into areas of relatively high CO coverage, and in this case, the phase change is more gradual and of lower amplitude. The propagation speed of these reaction waves is similar to those observed experimentally for CO and oxygen fronts [H. H. Rotermund et al., J. Chem. Phys. 91, 4942 (1989); H. H. Rotermund et al., Nature (London) 343, 355 (1990); J. Lauterbach and H. H. Rotermund, Surf. Sci. 311, 231 (1994)]. In the two-dimensional version of our model, the traveling waves take the form of target patterns emitted from surface inhomogeneities.     

Control of the excitability of neuronal tissue by weak external forces

The spreading depression (SD) is a pronounced example of excitation-depression waves in excitable media, to which neuronal tissue according to its structure and functions belongs. SD waves can especially easily be observed in the vertebrate retina which is neuronal tissue and a true part of the central nervous system (CNS). According to the high intrinsic optical signal (IOS) concomitant with the retinal spreading depression (rSD), it can be monitored with standard video imaging techniques, thus the retina has been used in our studies as a suitable model system for neuronal tissue in general. In particular, the control of wave set-up and propagation in excitable media by weak external forces is of high interest. Accordingly, the interaction of rSD waves with DC and AC electromagnetic fields of low amplitude and frequency and with gravity has been investigated in this study. The dependence of rSD-wave propagation velocity on the given parameters as one important indication of excitability control has been investigated in detail. Our results with rSD waves are partially compared to another well known excitable medium, the Belousov-Zhabotinsky reaction, where some data about the effects of electrical fields and gravity have already been published.     

Spatiotemporal chaos arising from standing waves in a reaction-diffusion system with cross-diffusion

We show that quasi-standing wave patterns appear in the two-variable Oregonator model of the Belousov-Zhabotinsky reaction when a cross-diffusion term is added, no wave instability is required in this case. These standing waves have a frequency that is half the frequency of bulk oscillations displayed in the absence of diffusive coupling. The standing wave patterns show a dependence on the systems size. Regular standing waves can be observed for small systems, when the system size is an integer multiple of half the wavelength. For intermediate sizes, irregular patterns are observed. For large sizes, the system shows an irregular state of spatiotemporal chaos, where standing waves drift, merge, and split, and also phase slips may occur.     

Interfaces in polymer blends

We investigate the structure and thermodynamics of interfaces in dense polymer blends using Monte Carlo (MC) simulations and self‐consistent field (SCF) calculations. For structurally symmetric blends we find quantitative agreement between the MC simulations and the SCF calculations for excess quantities of the interface (e.g., interfacial tension or enrichment of copolymers at the interface). However, a quantitative comparison between profiles across the interface in the MC simulations and the SCF calculations has to take due account of capillary waves. While the profiles in the SCF calculations correspond to intrinsic profiles of a perfectly flat interface the local interfacial position fluctuates in the MC simulations. We test this concept by extensive Monte Carlo simulations and study the cross‐over between “intrinsic” fluctuations which build up the local profile and capillary waves on long (lateral) length scales. Properties of structurally asymmetric blends are exemplified by investigating polymers of different stiffness. At high incompatibilities the interfacial width is not much larger than the persistence length of the stiffer component. In this limit we find deviations from the predictions of the Gaussian chain model: while the Gaussian chain model yields an increase of the interfacial width upon increasing the persistence length, no such increase is found in the MC simulations. Using a partial enumeration technique, however, we can account for the details of the chain architecture on all length scales in the SCF calculations and achieve good agreement with the MC simulations. In blends containing diblock copolymers we investigate the enrichment of copolymers at the interface and the concomitant reduction of the interfacial tension. At weak segregation the addition of copolymers leads to compatibilization. At high incompatibilities, the homopolymer‐rich phase can accommodate only a small fraction of copolymer before the copolymer forms a lamellar phase. The analysis of interfacial fluctuations yields an estimate for the bending rigidity of the interface. The latter quantity is important for the formation of a polymeric microemulsion at intermediate segregation and the consequences for the phase diagram are discussed.     

Protein adsorption on novel acrylamido-based polymeric ion-exchangers III. Salt concentration effects and elution behavior

The effect of salt concentration on the adsorption and desorption of BSA has been determined for a polymeric anion-exchanger based on acrylamido monomers. The material investigated possesses a high adsorption capacity at low salt concentration and the bound protein can be recovered quantitatively at high salt concentrations. The effects of salt on adsorption and desorption rates were evaluated from batch and shallow-bed experiments, and a model was developed to describe the data quantitatively. The adsorption capacity decreases as the salt concentration is increased, but both adsorption and desorption rates increase at higher salt concentrations. The predictability of the behavior of columns packed with this material was examined by comparing model predictions and experimental results obtained in laboratory columns. In general, a good agreement was obtained between predicted and experimental breakthrough and elution profiles, especially in shorter columns. Thus, the model allows a prediction of the effects of column length, mobile phase flow-rate, protein feed concentration, and salt concentration on dynamic capacity, productivity, and on the concentration of product fractions.     

Numerical approximation of a two-dimensional model of non-isothermal reactive liquid chromatography involving slow rates of adsorption–desorption kinetics

Abstract

A two-dimensional general rate model of non-isothermal reactive column chromatography is formulated considering homogenous and heterogeneous reaction rates, slow rates of adsorption–desorption kinetics, and enthalpies of adsorption and reaction. The model is expressed by a system of six nonlinear partial differential equations (PDEs) coupled with algebraic expressions for the adsorption and reaction rates. The nonlinearity of adsorption isotherm and reaction term hinders the derivation of analytical solutions. For that reason, a flux-limiting high-resolution finite volume scheme is suggested to numerically approximate the model equations. The effects of several kinetic and thermodynamic parameters are rigorously analyzed on the reactant conversion and components separation.     

Theory of ordering in three-dimensional polymer systems with local orientational-deformational interactions

The spontaneous ordering of a three-dimensional polymer system composed of flexible segments with a fixed mean-square length in the presence of local intra- and interchain orientational-deformational interactions was considered. The fixation of the segment chain length on average is possible only during relatively weak interchain interactions or at high temperatures, i.e., in the isotropic state. The three-dimensional model, unlike its two-dimensional version, suggests the existence of the critical point at which a second-order phase transition from the isotropic state to an ordered state takes place. The critical behavior of the multichain model is described by the spherical approximation for an anisotropic Heisenberg ferromagnetic. The dependence of the critical point and the parameters of short- and long-range dipole and quadrupole orientational orders on the chain rigidity and magnitude of interchain interactions was determined. In the isotropic state, orientation correlations of segments decline according to the Ornstein-Zernike law, as in the 3D model of Gaussian subchains without fixation of their mean-square length. In the ordered state, the correlation functions tend to a finite limiting value corresponding to the presence of long-range order, as in the case of the multichain model of rigidchain segments in the strong-order approximation. A comparison of the short-range and long-range orders in the model of chains composed of segments with a fixed mean-square length and undeformable (rodlike) elements in the mean-field approximation, on the one hand, and multichain models, on the other hand, showed their equivalence, especially at high degrees of ordering.     

具有平方衰减项的平方自催化开放系统中的化学波研究

建立了开放系统中伴随平方衰减反应的双分子自催化反应理论模型,给出了系统的动力学分析,在给定初边值下解的估计及存在化学波的必要条件、化学波波速的最小值及平方衰减项对化学波的影响.随着衰减系数的增加,平方衰减项逐步成为系统反应中化学波波形的决定因素.     

法拉第吸脱附偶联过程循环伏安行为的有限元分析

法拉第吸脱附偶联过程的电化学行为较为复杂,难以定量获得其表界面反应动力学信息. 本文通过COMSOL有限元软件对法拉第吸脱附偶联过程的循环伏安行为进行数值分析,研究了反应物或产物不同吸附条件下的循环伏安行为. 结果表明：当反应物或产物弱吸附时,可通过阴、阳极峰电流之差实现饱和吸附量的定量表征. 随着吸附平衡常数的增大,反应由弱吸附向强吸附过渡,峰电流由扩散峰与吸脱附峰相互重叠过渡到相互分离的吸脱附“前波”或“后波”特征. 该吸脱附特征峰的形状和位置与电势依赖的吸附平衡常数有关. 吸附平衡常数及其电势依赖程度越大,吸脱附峰偏离扩散峰越远,吸脱附峰越尖锐. 该模型为法拉第吸脱附偶联过程的循环伏安研究提供了一种定量研究方法,能够帮助研究者从复杂的吸脱附伏安行为中定量获得饱和吸附量和吸附平衡常数等信息,并对涉及吸脱附的电催化研究具有一定指导意义.     

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.     

CO在CeO2(111)表面的吸附与氧化

采用密度泛函理论计算了CO在CeO2(111)表面的吸附与氧化反应行为. 结果表明, O2在洁净的CeO2(111)表面为弱物理吸附, 而在氧空位表面是强化学吸附, 且O2分子活化程度较大, O—O键长为0.143 nm. CO在CeO2(111)表面吸附行为的研究表明, CO在洁净表面及氧空位表面上为物理吸附, 吸附能均小于0.42 eV; 当表面氧空位吸附O2后, CO可吸附生成二齿碳酸盐中间体或直接生成CO2, 与原位红外光谱结果相一致. 表面碳酸盐物种脱附生成CO2的能垒仅为0.28 eV. 计算结果表明, 当CeO2表面存在氧空位时, Hubbard参数U对CO吸附能有一定的影响. CeO2载体在氧化反应中可能的催化作用为, 在氧气氛下, CeO2表面氧空位吸附O2分子, 形成活性氧物种, 参与CO催化氧化反应.     

Fluorescence correlation spectroscopy at the oil-water interface: hard disk diffusion behavior in dilute beta-lactoglobulin layers precedes monolayer formation

We have performed a thorough characterization of fluorescence correlations spectroscopy (FCS) applied to oil-water interfaces of viscous oil droplets in aqueous solution, including numerical wave-optical calculations of the detection geometry and regularized multicomponent analysis of sample data. It is shown how significant errors in the estimation of the surface concentration can be avoided when FCS is applied to an interface region. We present data on the adsorption dynamics of beta-lactoglobulin (BLG), a well-studied model system. It is found that electrostatic repulsion slows the adsorption process and reduces the initial saturation density far below the monolayer concentration. During the first stages of adsorption, the diffusion coefficients of adsorbed protein closely follow the 2D hard disk model of Lahtinen et al.1 in response to increased surface concentration, which suggests that protein-protein interactions are limited to long-range Coulombic interactions at this stage.     

Structure of flexible and semiflexible polyelectrolyte chains in confined spaces of slit micro/nanochannels

Understanding the behavior of a polyelectrolyte in confined spaces has direct relevance in design and manipulation of microfluidic devices, as well as transport in living organisms. In this paper, a coarse-grained model of anionic semiflexible polyelectrolyte is applied, and its structure and dynamics are fully examined with Brownian dynamics (BD) simulations both in bulk solution and under confinement between two negatively charged parallel plates. The modeling is based on the nonlinear bead-spring discretization of a continuous chain with additional long-range electrostatic, Lennard-Jones, and hydrodynamic interactions between pairs of beads. The authors also consider the steric and electrostatic interactions between the bead and the confining wall. Relevant model parameters are determined from experimental rheology data on the anionic polysaccharide xanthan reported previously. For comparison, both flexible and semiflexible models are developed accompanying zero and finite intrinsic persistence lengths, respectively. The conformational changes of the polyelectrolyte chain induced by confinements and their dependence on the screening effect of the electrolyte solution are faithfully characterized with BD simulations. Depending on the intrinsic rigidity and the medium ionic strength, the polyelectrolyte can be classified as flexible, semiflexible, or rigid. Confined flexible and semiflexible chains exhibit a nonmonotonic variation in size, as measured by the radius of gyration and end-to-end distance, with changing slit width. For the semiflexible chain, this is coupled to the variations in long-range bond vector correlation. The rigid chain, realized at low ionic strength, does not have minima in size but exhibits a sigmoidal transition. The size of confined semiflexible and rigid polyelectrolytes can be well described by the wormlike chain model once the electrostatic effects are taken into account by the persistence length measured at long length scale.     

Equilibrium adsorption data from temperature-programmed desorption experiments

This work describes a novel method that enables the calculation of a series of adsorption isotherms basically from a single Temperature-Programmed Desorption (TPD) experiment. The basic idea is to saturate an adsorbent packed in a fixed bed at a certain feed concentration and temperature and to subsequently increase its temperature linearly with time, while maintaining a constant feed concentration.We measured TPD response curves for carbon dioxide on activated carbon at different heating rates for various combinations of feed concentration, molar flow rate and particle size. Response curves from an axially dispersed plug flow model were fitted to experimental data by adjustment of the Langmuir parameters. Adsorption isotherms calculated with these fitted parameters are in good agreement with adsorption data obtained by other methods over the full temperature range.The influence of heating rate on intraparticle mass transfer resistance is discussed.     

Proximal adsorption at glass surfaces: ionic strength, pH, chain length effects

The adsorption and desorption of pyridinium chloride surfactants on borosilicate glass are studied as a function of the separation between two glass-solution interfaces. Both the adsorption and desorption change exponentially with the separation; the decay is equal to the solution Debye length. Changes in adsorption are smaller at pH 1.8 (near the point of zero charge of glass) than at pH 6. These results are consistent with an electrostatic cause for the changes in adsorption. The magnitude of the adsorption regulation, however, depends on the length of the alkyl chain and the surface excess of the surfactant. Therefore, proximal adsorption in this system depends on the coupling between the long-range electrostatic forces and the short-range chain-chain interactions. The equation of state for the surfactant on a regulating surface is discussed with respect to changes in intersurface separation.     

First principles investigations of Pd-on-Au nanostructures for trichloroethene catalytic removal from groundwater

Catalytic groundwater remediation from chlorinated organic solvents like trichloroethene (TCE) has been found to be more effective and sustainable than traditional non-destructive methods. Among the experimentally studied catalyst materials, Pd-decorated Au nanoparticles show the highest activity and selectivity combined with the best resistance towards poisoning by chemicals present in groundwater. In this study the thermochemistry and adsorption geometries of TCE and its hydrodechlorination products are investigated via density functional theory calculations. Various model systems for Pd-supported Au nanoparticles are addressed. The adsorption of TCE is endothermic on bare Au(111), almost thermoneutral or slightly exothermic on Pd-Au surface alloys and clearly exothermic on Pd overlayer structures on Au(111). The strongest chemisorption is on the di-σ configuration between Pd atoms over the smallest 2D Pd clusters containing only a few Pd atoms. These are not, however, the best catalysts as they are too small to co-adsorb hydrogen needed for hydrodechlorination reaction. We demonstrate good correlation between adsorption energies and the d-band center of the system. The variation of adsorption energy from the one Pd-Au composition to the other can be tentatively assigned to be due to the ligand and coordination effects. Also, the ensemble effects are important; without the right ensemble the adsorption is weak or endothermic.     

Examining the accuracy of ideal adsorbed solution theory without curve-fitting using transition matrix Monte Carlo simulations

Ideal adsorbed solution theory (IAST) is a well-known approach to predicting multicomponent adsorption isotherms in microporous materials from experimental or simulation data for single-component adsorption. A limitation in practical applications of IAST is that useful calculations often require extrapolation of fitted single-component isotherms beyond the range for which data are available. We introduce a molecular simulation approach in which the intrinsic accuracy of IAST can be examined in a context that avoids any need to perform curve fitting with single-component data. Our approach is based on using transition matrix Monte Carlo to define single-component adsorption isotherms for arbitrary bulk-phase pressures from a single simulation. We apply our approach to several light gas mixtures in silica zeolites and a carbon nanotube to examine the intrinsic accuracy of IAST for these model systems.     

Surface vibration induced spatial ordering of periodic polymer patterns on a substrate

We demonstrate the possibility of producing regular, long-range, spatially ordered polymer patterns without requiring the use of physical or chemical templating through the interfacial destabilization of a thin polymer film driven by surface acoustic waves (SAWs). The periodicity and spot size of the pattern are observed to be dependent on a single parameter, that is, the SAW frequency (or wavelength), therefore offering a rapid, simple, yet novel method for self-organized regular spatial polymer pattern formation that is far more tunable than conventional polymer patterning procedures.