Propagation of photosensitive chemical waves on the circular routes

The propagation of chemical waves in the photosensitive Belousov-Zhabotinsky (BZ) reaction was investigated using an excitable field in the shape of a circular ring or figure "8" that was drawn by computer software and then projected on a film soaked with BZ solution using a liquid-crystal projector. For a chemical wave in a circular reaction field, the shape of the chemical wave was investigated depending on the ratio of the inner and outer radii. When two chemical waves were generated on a field shaped like a figure "8" (one chemical wave in each circle) as the initial condition, the location of the collision of the waves either was constant or alternated depending on the degree of overlap of the two circular rings. These experimental results were analyzed on the basis of a geometrical discussion and theoretically reproduced on the basis of a reaction-diffusion system using a modified Oregonator model. These results suggest that the photosensitive BZ reaction may be useful for creating spatio-temporal patterns depending on the geometric arrangement of excitable fields.     

Characteristic features in the collision of chemical waves depending on the aspect ratio of a rectangular field

The photosensitive Belousov-Zhabotinsky (BZ) reaction was investigated on a double rectangular field composed of two rectangular routes, which was drawn using computer software and then projected using a liquid-crystal projector on a filter paper soaked with BZ solution. When two chemical waves were generated on the rectangular routes as the initial condition, the nature of the collision of the waves could be theoretically classified into four categories depending on the initial phase difference between the two waves and the aspect ratio of the rectangular routes. The experimental results were consistent with the features of the theoretical prediction. These results suggest that the feature of wave propagation characteristically develops depending on the geometry of the excitable fields.     

Coexistence of wave propagation and oscillation in the photosensitive Belousov-Zhabotinsky reaction on a circular route

The photosensitive Belousov-Zhabotinsky (BZ) reaction was investigated on a circular ring, which was drawn using computer software and then projected on a film soaked with BZ solution using a liquid-crystal projector. Under the initial conditions, a chemical wave propagated with a constant velocity on the black ring under a bright background. When the background was rapidly changed to dark, coexistence of the oscillation on part of the ring and propagation of the chemical wave on the other part was observed. These experimental results are discussed in relation to the nature of the photosensitive BZ reaction and theoretically reproduced based on a reaction-diffusion system using the modified Oregonator model.     

Photoexcited chemical wave in the ruthenium-catalyzed Belousov-Zhabotinsky reaction

The excitation of the photosensitive Belousov-Zhabotinsky (BZ) reaction induced by light stimulation was systematically investigated. A stepwise increase in the light intensity induced the excitation, whereas a stepwise decrease did not induce the excitation. The threshold values for the excitation were found to be a function of the initial and final light intensities, time variation in light intensity, and the concentration of NaBrO(3). The experimental results were qualitatively reproduced by a theoretical calculation based on a three-variable Oregonator model modified for the photosensitive BZ reaction. These results suggest that although the steady light irradiation is known to inhibit oscillation and chemical waves in the BZ system under almost all conditions, the stepwise increase in the light irradiation leads to the rapid production of an activator, resulting in the photoexcitation.     

光敏性BZ反应的时空动力学

作为研究非线性时空动力学最理想的化学反应体系之一,三联(2,2'-联吡啶)钌(Ⅱ)(Ru(bpy)₃²⁺)为催化剂的Belousov-Zhabotinsky (BZ)振荡反应具有独特的光敏特性并能呈现丰富的时空动力学行为。研究光控BZ反应有助于我们对一系列物理、化学和生命体系中复杂动力学现象的理解。本文综述了不同实验条件下光效应对钌催化BZ反应均相复杂振荡和空间反应扩散化学波的影响, 以及光响应BZ反应与软物质耦合体系的复杂动力学行为,在此基础上介绍光抑制和光诱导反应机理和模型。对光控BZ反应体系存在的问题和发展方向进行了探讨。     

Estimation of the activation energy in the Belousov-Zhabotinsky reaction by temperature effect on excitable waves

We report the temperature effect on the propagation of excitable traveling waves in a quasi-two-dimensional Belousov-Zhabotinsky reaction-diffusion system. The onset of excitable waves as a function of the sulfuric acid concentration and temperature is identified, on which the sulfuric acid concentration exhibits an Arrhenius dependence on temperature. On the basis of this experimental data, the activation energy of the self-catalyzed reaction in the Oregonator model is estimated to be 83-113 kJ/mol, which is further supported by our numerical simulations. The estimation proceeds without analyzing detailed reaction steps but rather through observing the global dynamic behaviors in the BZ reaction. For a supplement, the wave propagation velocities are calculated based on our results and compared with the experimental observations.     

Chemical waves

In our paper we try to describe the basic concepts of chemical waves and spatial pattern formation in a simple way. We pay particular attention to self-organisation phenomena in extended excitable systems. These result in the appearance of travelling waves, spiral waves, target patterns, Turing structures or more complicated structures called scroll waves, which are three-dimensional systems. We describe the most famous oscillating reaction, the Belousov-Zhabotinsky (BZ) reaction, in greater detail. This is because it is of great interest in both physical chemistry and in studies on the evolution and sustenance of self-organising biological systems.     

In situ 1H NMR Imaging Study of Propagation of Concentration Waves in an Autocatalytic Reaction in a Fixed Granular Bed

The in situ ¹H NMR technique was used to study the propagation of chemical waves during the liquid-phase Belousov–Zhabotinsky (BZ) reaction in a model fixed bed of grains consisting of chemically inert glass beads or quartz sand. The propagation of autocatalytic chemical waves in this bed is determined by the size of pores between the grains. The rate of wave front propagation is independent of the size of the grains involved in this bed but is much lower than that in the bulk of the homogenous aqueous phase. This may be attributed to the difference in the effective diffusion coefficients in the homogeneous liquid phase and in the bed.     

Macroscopic dynamics as reporter of mesoscopic organization: the Belousov-Zhabotinsky reaction in aqueous layers of DPPC lamellar phases

The propagation of traveling chemical waves in the excitable Belousov-Zhabotinsky (BZ) system when performed in the presence of 1,2-dipalmitoyl-sn-glycero-3-phosphatidyl choline (DPPC) bilayers responds sensitively to the phospholipid content. The characteristic features of wave propagation, such as spiral pitch, rotation period, and size of the spiral core region, show two regions of different behavior, one below and the other above a DPPC content of 12.5% (w/w) thus suggesting a transition in the organization of the lipid domains at a DPPC content of ～12.5% (w/w). This transition is supported by small-angle X-ray scattering data, which show pronounced changes in the coherence lengths of the lyotropic smectic domains. Thus, the dynamics of the chemical system occurring at a macroscopic length scale reflects the organization of the water/lipid domains which extend over mesoscopic lengths. These findings indicate that in the BZ/DPPC system, there is an interaction between processes that occurs at length scales differing by as much as 3 orders of magnitude.     

Density changes accompanying wave propagation in the cerium-catalyzed Belousov-Zhabotinsky reaction

Refractive index measurement using an interferometric imaging system and observation of chemical wave shapes were carried out during chemical wave propagation of a cerium-catalyzed Belousov-Zhabotinsky (BZ) reaction. Densities increased as chemical waves propagated in samples without NaBr, and decreased in samples with NaBr. Concentration changes of malonic acid, bromomalonic acid, and BrO3- were estimated from Raman spectral measurements in a stirred batch BZ reaction, and these also exhibited differences between samples with and without NaBr. It is proposed that a reaction subset yielding low molecular weight carboxylic acids is predominant in samples with NaBr, whereas a pathway leading to dibromoacetic acid or tribromoacetic acid production is the major process in samples without NaBr.     

Light‐Modulated Intermittent Wave Groups in a Diffusively Fed Reactive Gel

Inspired by the biological growth that takes place in time‐varying external fields such as light or temperature, we design an open reaction‐diffusion system in order to investigate growth dynamics. The system is composed of the Belousov–Zhabotinsky (BZ) oscillatory reaction coupled with a copolymer gel consisting of NIPAAm and a photosensitive ruthenium catalyst. When subject to a unidirectional flow of the BZ reactants, the system displays groups of chemical waves whose structure depends upon the period and amplitude of illumination. Simulations of a modified six‐variable Oregonator model exhibit all the complex wave groups found in our experiments. Studying this growth structure may aid in understanding the influence of periodic environmental variation on complex growth processes in living systems.     

An elegant method to study an isolated spiral wave in a thin layer of a batch Belousov-Zhabotinsky reaction under oxygen-free conditions

A method to prepare a uniform thin layer of a batch Belousov-Zhabotinsky (BZ) reaction under oxygen-free conditions for the study of an isolated spiral wave is presented. After a first layer of gel soaked with the BZ solution has been delivered into the reactor, a single spiral wave was initiated, and finally the remaining reactor volume was filled with gel and BZ medium. The completely filled reactor is sealed gas-tightly, yielding oxygen-free, and thus more controlled, reaction conditions. A systematic study of the behaviour of an isolated spiral wave in a ferroin-catalyzed BZ reaction under batch conditions has been performed. Recipes for BZ media that support a slowly rotating meandering spiral were developed. In cases of extremely low excitability (i.e., relative large stimuli are required to induce a propagating wave), the number of petals in the trajectory of a spiral tip decreased due to aging of the reaction system. Since oxygen-free conditions are necessary for the study of the dynamics in three-dimensional excitable media, and the wave velocities of a spiral are sufficiently low, the developed chemical recipes are suitable for studies of the behaviour of scroll waves in three-dimensional systems by optical tomography.     

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.     

Synthesis of monodisperse silica microspheres and modification with diazoresin for mixed‐mode ultra high performance liquid chromatography separations

Monodisperse silica particles with average diameters of 1.9–2.9 μm were synthesized by a modified Stöber method, in which tetraethyl orthosilicate was continuously supplied to the reaction mixture containing KCl electrolyte, water, ethanol, and ammonia. The obtained silica particles were modified by self‐assembly with positively charged photosensitive diazoresin on the surface. After treatment with ultraviolet light, the ionic bonding between silica and diazoresin was converted into covalent bonding through a unique photochemistry reaction of diazoresin. Depending on the chemical structure of diazoresin and mobile phase composition, the diazoresin‐modified silica stationary phase showed different separation mechanisms, including reversed phase and hydrophilic interactions. Therefore, a variety of baseline separation of benzene analogues and organic acids was achieved by using the diazoresin‐modified silica particles as packing materials in ultra high performance liquid chromatography. According to the π–π interactional difference between carbon rings of fullerenes and benzene rings of diazoresin, C₆₀ and C₇₀ were also well separated by ultra‐high performance liquid chromatography. Because it has a small size, the ∼2.5 μm monodisperse diazoresin‐modified silica stationary phase shows ultra‐high efficiency compared with the commercial C₁₈‐silica high‐performance liquid chromatography stationary phase with average diameters of ∼5 μm.     

Liquid Marble Photosensor

A liquid marble is a liquid droplet coated by a hydrophobic powder. The liquid marble does not wet adjacent surfaces and therefore can be manipulated as a dry soft body. A Belousov-Zhabotinsky (BZ) reaction is an oscillatory chemical reaction exhibiting waves of oxidation. We demonstrate how to make a photo-sensor from BZ medium liquid marbles. We insert electrodes into a liquid marble, prepared from BZ solution and coated with polyethylene powder. The electrodes record a potential difference which oscillates due to oxidation wave-fronts crossing the electrodes. When the BZ marble is illuminated by a light source, the oxidation wave-fronts are hindered and, thus, the electrical potential recorded ceases to oscillate. We characterise several types of responses of BZ marble photosensors to various stimuli, and provide explanations of the recorded activity. BZ liquid marble photosensors may find applications in the fields of liquid electronics, soft robotics and unconventional computing.     

Experimental Investigation of the Dynamical Modes of Four Pulse-Coupled Chemical Micro-Oscillators

We present an experimental system of four identical microreactors (MRs) in which the photosensitive oscillatory Belousov-Zhabotinsky (BZ) reaction occurs. The inhibitory coupling of these BZ MRs is organized via pulses of light coming to each MR from a computer projector. These pulses are induced by spike(s) in other MR(s) of the same network. Time delay between the spike in one BZ MR and the pulsed perturbation of the other BZ MR(s), the amplitude of light pulses, their duration, and the connectivity of the MRs are controlled by the LabVIEW software. Recording the dynamics of the BZ reaction in the MRs via a microscope equipped with a CCD camera, we observe all the main dynamical modes of our network of MRs, which are the IP (in-phase), AP (anti-phase), W (walk), and WR (walk reverse) for the unidirectional coupling, and the IP, two-cluster, three-cluster, and splay modes for the all-to-all coupling. Our software detects all the modes of the network automatically and makes it possible to switch between them on demand using a few special “switching” pulses. As the result of the present work, the experimental implementation of the adaptive behaviour of the pulse-coupled chemical micro-oscillator networks becomes available.     

Model study of synchronization and other phenomena in light perturbation of the Briggs–Rauscher reaction

Calculations are performed to model several phenomena observed when a photosensitive oscillating chemical reaction, the Briggs–Rauscher (BR) reaction, is subject to irradiation in a continuous-flow stirred-tank reactor. The BR mechanism proposed earlier by De Kepper and Epstein is supplemented by additional steps involving the photogeneration and subsequent reaction of iodine atoms. The calculations show qualitative agreement with the following experimentally observed phenomena: (a) change in the period and amplitude of oscillation as a function of the intensity of constant illumination, (b) synchronization between periodically varying illumination and the period of chemical oscillation, (c) phase shifts induced by single light pulses, and (d) dark steady states which are excitable by single light pulses and become oscillatory at appropriate levels of constant illumination.     

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.     

Dissipative structures in systems of diffusion-bonded chemical nano- and micro oscillators

In spatially extended classical Belousov-Zhabotinsky (BZ) reaction, trigger spiral or concentric waves usually occur. If the BZ reaction is dispersed into nanodroplets of water-in-oil emulsion, new patterns are observed such as standing waves, anti-spirals, oscillons, dash-waves, jumping waves, Turing patterns, and other. If the size of water droplets is increased up to tens of micrometers, coupled micro-oscillators produce new stationary and oscillatory discrete dissipative patterns. In the review, comparative analysis of these patterns is done and a possibility of creating a chemical computer on the basis of dissipative patterns is discussed.     

Direction control of chemical wave propagation in self-oscillating gel array

A chemomechanical actuator utilizing a reaction-diffusion wave across gap junction was constructed toward a novel mircoconveyer by micropatterned self-oscillating gel array. Unidirectional propagation of the chemical wave of the Belousov-Zhabotinsky (BZ) reaction was induced on gel arrays. In the case of using a triangle-shaped gel as an element of the array, the chemical wave propagated from the corner side of the triangle gel to the plane side of the other gel (C-to-P) across the gap junction, whereas it propagated from the plane side to the corner side (P-to-C) in the case of the pentagonal gel array. Numerical analysis based on the Keener-Tyson model was done for understanding the mechanism of unidirectional propagation in triangle and pentagonal gel arrays. The swelling and deswelling changes of the gels followed the unidirectional propagation of the chemical wave.