Oregonator Model Research Articles

Effect of electric field chirality on the unpinning of chemical waves in the Belousov–Zhabotinsky reaction

We investigate the unpinning of chemical spiral waves attached to obstacles in the Belousov–Zhabotinsky (BZ) reaction using a Circularly Polarized Electric Field (CPEF). The unpinning is quantified by measuring the angle at which the spiral leaves the obstacle. Previously, we had found that the wave can unpin when the electric field along the direction of the spiral is above a threshold value. When we apply a DC field, this condition can be satisfied for a range of spiral phases, which we call the unpinning window (UW). With a CPEF, this UW moves either along the direction of the spiral (co-rotating) or against the spiral (counter-rotating). We find that when the field is co-rotating, it can take several rotations of the spiral to get unpinned. With a counter-rotating field, the spiral always unpins during the first rotation. We analyze how unpinning with CPEF depends on the electric field’s relative speed, chirality, and strength using experiments and the Oregonator model. Our work helps to understand and control chemical waves.

Hopf bifurcation and limit cycle of the two‐variable Oregonator model for Belousov–Zhabotinsky reaction

This paper is concerned with a two‐variable Oregonator model for Belousov–Zhabotinsky Reaction. Llibre and Oliveira (2022) proved that Oregonator model with an unstable node or focus has at least one limit cycle in the positive quadrant, and the system has a unique stable limit cycle for some values of the parameters. It is shown in the present paper that the positive equilibrium is not a center, and that if the system has a positive equilibrium which is a weak focus, then its order is at most 2. There exist some parameter values such that system has small limit cycle around the positive equilibrium.

Analysis, Symmetry and Asymptotic Behaviour of Solutions for the Belousov-Zhabotinsky Model

This research provides analytical insights in connection with the solutions of the Oregonator model, a refined iteration of the iconic Belousov-Zhabotinsky (BZ) reaction problem. This chemical process, initially observed by B. P. Belousov while replicating the Krebs cycle in vitro and later modified by Zhabotinsky using Fe-phenanthroline (ferroin), has become a hallmark example of non-linear dynamics, chaos theory, and has parallels in various biological systems. Our study systematically delves into the boundedness, regularity, and possible symmetries of weak solutions. We explore traveling waves using the Tanh-method, alongside examining asymptotic solutions entrenched in self-similar forms and exponential scaling leading to a Hamilton-Jacobi equation. This research emphasizes on mathematical arguments along with the dynamics of the involved chemical concentrations. We provide new forms of analytical solutions showing them in a comprehensive manner that connects with the interpretation of the Oregonator model and its broader implications in chemical systems.

KCC Theory of the Oregonator Model for Belousov-Zhabotinsky Reaction

The behavior of the simplest realistic Oregonator model of the BZ-reaction from the perspective of KCC theory has been investigated. In order to reduce the complexity of the model, we initially transformed the first-order differential equation of the Oregonator model into a system of second-order differential equations. In this approach, we describe the evolution of the Oregonator model in geometric terms, by considering it as a geodesic in a Finsler space. We have found five KCC invariants using the general expression of the nonlinear and Berwald connections. To understand the chaotic behavior of the Oregonator model, the deviation vector and its curvature around equilibrium points are studied. We have obtained the necessary and sufficient conditions for the parameters of the system in order to have the Jacobi stability near the equilibrium points. Further, a comprehensive examination was conducted to compare the linear stability and Jacobi stability of the Oregonator model at its equilibrium points, and We highlight these instances with a few illustrative examples.

Effect of excitability on partially pinned scroll waves in excitable chemical media.

We present an investigation of excitability effects on the dynamics of scroll waves partially pinned to inert cylindrical obstacles in three-dimensional Belousov-Zhabotinsky excitable media. We also report on corresponding numerical simulations with the Oregonator model. The excitability varies according to the concentration of sulfuric acid [H_{2}SO_{4}] in the Belousov-Zhabotinsky (BZ) reaction and the parameter ɛ^{-1} in the Oregonator model. Initially, the freely rotating scroll segment rotates faster than the pinned one. The difference in the frequency of the two parts results in a transition from a straight pinned scroll wave to a twisted one, which helically wraps around the entire obstacle. The wave frequency in the whole volume is equal to that of the freely rotating scroll wave. When the excitability is increased, the time for the transition to the twisted wave structure decreases while the average speed s of the development increases. After the transition, the twisted wave remains stable. In media with higher excitability, the helical pitch is shorter but the twist rate ω is higher. Analysis presented in this study together with our previous findings of the effect of the cylindrical obstacle diameter on the wave dynamics results in common features: The average speed s and the twist rate ω of both studies fit well to functions of the difference in the initial frequency Δf of the freely rotating and untwisted pinned waves. We also demonstrate the robustness of the partially pinned scroll waves against perturbations from spontaneous waves emerging during the wave generation in the BZ medium with high [H_{2}SO_{4}]. Even though the scroll wave is partly disturbed at the beginning of the experiment, the spontaneous waves are gradually suppressed and the typical wave structure is finally developed.

Numerical methods for control-based continuation of relaxation oscillations

Control-based continuation (CBC) is an experimental method that can reveal stable and unstable dynamics of physical systems. It extends the path-following principles of numerical continuation to experiments and provides systematic dynamical analyses without the need for mathematical modelling. CBC has seen considerable success in studying the bifurcation structure of mechanical systems. Nevertheless, the method is not practical for studying relaxation oscillations. Large numbers of Fourier modes are required to describe them, and the length of the experiment significantly increases when many Fourier modes are used, as the system must be run to convergence many times. Furthermore, relaxation oscillations often arise in autonomous systems, for which an appropriate phase constraint is required. To overcome these challenges, we introduce an adaptive B-spline discretisation that can produce a parsimonious description of responses that would otherwise require many Fourier modes. We couple this to a novel phase constraint that phase-locks control target and solution phase. Results are demonstrated on simulations of a slow-fast synthetic gene network and an Oregonator model. Our methods extend CBC to a much broader range of systems than have been studied so far, opening up a range of novel experimental opportunities on slow-fast systems.

Influence of a circular obstacle on the dynamics of stable spiral waves with straining

The current study envisages to investigate numerically, probably for the first time, the combined effect of a circular obstacle and medium motion on the dynamics of a stable rotating spiral wave. A recently reconstructed spatially fourth and temporally second order accurate, implicit, unconditionally stable high order compact scheme has been employed to carry out simulations of the Oregonator model of excitable media. Apart from studying the effect of the stoichiometric parameter, we provide detailed comparison between the dynamics of spiral waves with and without the circular obstacles in the presence of straining effect. In the process, we also inspect the dynamics of rigidly rotating spiral waves without straining effect in presence of the circular obstacle. The presence of the obstacle was seen to trigger transition to non-periodic motion for a much lower strain rate.

Information Processing Using Networks of Chemical Oscillators.

I believe the computing potential of systems with chemical reactions has not yet been fully explored. The most common approach to chemical computing is based on implementation of logic gates. However, it does not seem practical because the lifetime of such gates is short, and communication between gates requires precise adjustment. The maximum computational efficiency of a chemical medium is achieved if the information is processed in parallel by different parts of it. In this paper, I review the idea of computing with coupled chemical oscillators and give arguments for the efficiency of such an approach. I discuss how to input information and how to read out the result of network computation. I describe the idea of top-down optimization of computing networks. As an example, I consider a small network of three coupled chemical oscillators designed to differentiate the white from the red points of the Japanese flag. My results are based on computer simulations with the standard two-variable Oregonator model of the oscillatory Belousov–Zhabotinsky reaction. An optimized network of three interacting oscillators can recognize the color of a randomly selected point with >98% accuracy. The presented ideas can be helpful for the experimental realization of fully functional chemical computing networks.

Discontinuous stationary solutions to certain reaction-diffusion systems

Systems consisting of a single ordinary differential equation coupled with one reaction-diffusion equation in a bounded domain and with the Neumann boundary conditions are studied in the case of particular nonlinearities from the Brusselator model, the Gray-Scott model, the Oregonator model and a certain predator-prey model. It is shown that the considered systems have the both smooth and discontinuous stationary solutions, however, only discontinuous ones can be stable.

The Concilium of Information Processing Networks of Chemical Oscillators for Determining Drug Response in Patients With Multiple Myeloma.

It can be expected that medical treatments in the future will be individually tailored for each patient. Here we present a step towards personally addressed drug therapy. We consider multiple myeloma treatment with drugs: bortezomib and dexamethasone. It has been observed that these drugs are effective for some patients and do not help others. We describe a network of chemical oscillators that can help to differentiate between non-responsive and responsive patients. In our numerical simulations, we consider a network of 3 interacting oscillators described with the Oregonator model. The input information is the gene expression value for one of 15 genes measured for patients with multiple myeloma. The single-gene networks optimized on a training set containing outcomes of 239 therapies, 169 using bortezomib and 70 using dexamethasone, show up to 71% accuracy in differentiating between non-responsive and responsive patients. If the results of single-gene networks are combined into the concilium with the majority voting strategy, then the accuracy of predicting the patient’s response to the therapy increases to ∼ 85%.

Science, serendipity, coincidence, and the Oregonator at the University of Oregon, 1969–1974

This historical review of the development of the Oregonator model of the Belousov–Zhabotinsky reaction is based on a lecture Dick Field presented during IrvFest2015—Celebrating a founding father of chaos!, a meeting in commemoration of Irving R. Epstein’s 70th birthday. For Dick’s 80th birthday festschrift, we focus here on the five papers in the series named “Oscillations in chemical systems,” published in 1972 [Noyes et al., J. Am. Chem. Soc. 94, 1394–1395 (1972); Field et al., J. Am. Chem. Soc. 94, 8649–8664 (1972); Field and Noyes, Nature 237, 390–392 (1972)] and 1974 [Field and Noyes, J. Chem. Phys. 60, 1877–1884 (1974); Field and Noyes, J. Am. Chem. Soc. 96, 2001–2006 (1974)].

Intermittency regimes of poorly-mixed chemical oscillators

Perfect mixing or interaction between oscillators is almost never achieved under experimental conditions and, nevertheless, it might be crucial in understanding the observed phenomena. We propose a mathematical model that directly introduces the degree of mixing and analyze the consequences on the synchronization patterns observed. For that we considered catalyst-loaded chemical oscillators as they represent a paradigm for synchronization phenomena from the experimental and numerical point of view. In this study we explore a modified 3-variable Oregonator model where the active surrounding solution is discretized as oscillators themselves and a discrete radius of chemical exchange is introduced to account for spatial distribution and movement dynamics. We found that for low-to none levels of mixing in the system, a series of irregular states appear on the edge of phase transitions among dynamical regimes, and that several novel non-fully synchronized behaviors appear for a small window in the parameter space.

Computing With Networks of Chemical Oscillators and its Application for Schizophrenia Diagnosis.

Chemical reactions are responsible for information processing in living organisms, yet biomimetic computers are still at the early stage of development. The bottom-up design strategy commonly used to construct semiconductor information processing devices is not efficient for chemical computers because the lifetime of chemical logic gates is usually limited to hours. It has been demonstrated that chemical media can efficiently perform a specific function like labyrinth search or image processing if the medium operates in parallel. However, the number of parallel algorithms for chemical computers is very limited. Here we discuss top-down design of such algorithms for a network of chemical oscillators that are coupled by the exchange of reaction activators. The output information is extracted from the number of excitations observed on a selected oscillator. In our model of a computing network, we assume that there is an external factor that can suppress oscillations. This factor can be applied to control the nodes and introduce input information for processing by a network. We consider the relationship between the number of oscillation nodes and the network accuracy. Our analysis is based on computer simulations for a network of oscillators described by the Oregonator model of a chemical oscillator. As the example problem that can be solved with an oscillator network, we consider schizophrenia diagnosis on the basis of EEG signals recorded using electrodes located at the patient’s scalp. We demonstrated that a network formed of interacting chemical oscillators can process recorded signals and help to diagnose a patient. The parameters of considered networks were optimized using an evolutionary algorithm to achieve the best results on a small training dataset of EEG signals recorded from 45 ill and 39 healthy patients. For the optimized networks, we obtained over 82% accuracy of schizophrenia detection on the training dataset. The diagnostic accuracy can be increased to almost 87% if the majority rule is applied to answers of three networks with different number of nodes.

Self-oscillations in a certain Belousov–Zhabotinsky model

We consider the dynamic properties of a system of three differential equations known as the oreganator model. This model depends on four external parameters and describes one of the periodic Belousov–Zhabotinsky reactions. We obtain broad conditions for the parameters that ensure the existence of nonstationary steady-state regimes in oregonator model. With classical values of the parameters, the localization of the limit (at a long time) dynamics in the phase space has been improved. In fact, using numerical analysis, we significantly narrow the bounded region of the phase space containing the trajectories of the system. An iterative procedure is proposed for the approximate localization of closed trajectories (cycles) of the system on algebraic surfaces inR3. A promising problem of theoretical substantiation of the numerical convergence of this procedure is posed.

Bifurcation Caused by Delay in a Fractional-Order Coupled Oregonator Model in Chemistry

Establishing dynamical models to characterize the relation of different chemical compositions is an important topic in chemistry and mathematics. However, a lot of dynamical models are merely concerned with the integer-order dynamical models. The report on fractional-order chemical dynamical systems is quite few. In this current article, based on the earlier publications, we establish a new fractional-order coupled Oregonator model incorporating time delay. A set of sufficient conditions which ensure the stability and the onset of Hopf bifurcation of fractional-order coupled Oregonator model incorporating time delay are derived by regarding the time delay as bifurcation parameter. The exploration manifests that time delay has a vital influence on stabilizing system and controlling bifurcation of the investigated fractional-order coupled Oregonator model. At last, Matlab simulation results are adequately displayed to corroborate the derived theoretical achievements.

Instability of the Homogeneous Distribution of Chemical Waves in the Belousov-Zhabotinsky Reaction.

Chemical traveling waves play an important role in biological functions, such as the propagation of action potential and signal transduction in the nervous system. Such chemical waves are also observed in inanimate systems and are used to clarify their fundamental properties. In this study, chemical waves were generated with equivalent spacing on an excitable medium of the Belousov–Zhabotinsky reaction. The homogeneous distribution of the waves was unstable and low- and high-density regions were observed. In order to understand the fundamental mechanism of the observations, numerical calculations were performed using a mathematical model, the modified Oregonator model, including photosensitive terms. However, the homogeneous distribution of the traveling waves was stable over time in the numerical results. These results indicate that further modification of the model is required to reproduce our experimental observations and to discover the fundamental mechanism for the destabilization of the homogeneous-distributed chemical traveling waves.

Asymptotic limit-cycle analysis of oscillating chemical reactions

The asymptotic limit-cycle analysis of mathematical models for oscillating chemical reactions is presented. In this work, after a brief presentation of mathematical preliminaries applied to the biased Van der Pol oscillator, we consider a two-dimensional model of the Chlorine dioxide Iodine Malonic-Acid (CIMA) reactions and the three-dimensional and two-dimensional Oregonator models of the Belousov–Zhabotinsky reactions. Explicit analytical expressions are given for the relaxation-oscillation periods of these chemical reactions that are accurate within 5% of their numerical values. In the two-dimensional CIMA and Oregonator models, we also derive critical parameter values leading to canard explosions and implosions in their associated limit cycles.

The role of activation enthalpy modeled with a modified Arrhenius equation in a variant of a minimal bromate oscillator for temperatures changes

Abstract Belousov-Zhabotinsky chemical reactions and new variants were developed and studied at 277.5 K, 296.15 K, and 341.15 K using potassium bromate, sodium bromide, malonic acid, and ferroin as an indicator for the oscillating reaction. This reaction type is a minimal oscillator, which belongs to the fifth “uncatalyzed” family known as minimal bromate oscillators. A mathematical model is a proposal from the reaction mechanism of Zhabotinsky, the Oregonator model, and the modified Arrhenius equation. The control parameters of the mathematical model are the activation enthalpies of the oscillating reaction. Experimental and numerical results at 341.15 K show an increase in the amplitude and frequency of chemical oscillations and a decrease in the total oscillation time, while at 277.15 K the opposite mechanism happens.

Pattern Recognition of Chemical Waves: Finding the Activation Energy of the Autocatalytic Step in the Belousov-Zhabotinsky Reaction.

The Belousov–Zhabotinsky (BZ) reaction is an example of a homogeneous, nonequilibrium reaction used commonly as a model for the study of biological structure and morphogenesis. We report the experimental effects of temperature on spontaneously nucleated trigger waves in a quasi-two-dimensional BZ reaction–diffusion system, conducted isothermally at temperatures between 9.9 and 43.3 °C. Novel application of filter-coupled circle finding and localized pattern analysis is shown to allow the highly accurate extraction of average radial wave velocity and nucleation period. Using this, it is possible to verify a strong Arrhenius dependence of average wave velocity with temperature, which is used to find the effective activation energy of the reaction in accordance with predictions elaborated from the widely used Oregonator model of the BZ reaction. On the basis of our experimental results and existing theoretical models, the value for activation energy of the important self-catalyzed step in the Oregonator model is determined to be 86.58 ± 4.86 kJ mol–1, within range of previous theoretical prediction.

Bifurcation dynamics in a fractional-order oregonator model including time delay

Setting up mathematical models to describe the interaction of chemical variables has been a hot issue in chemical and mathematical areas. Nevertheless, many mathematical models are only involved with the integer-order differential equation case. The fruits on fractional-order chemical models are very scarce. In this present work, on the basis of the previous studies, we set up a novel fractional-order delayed Oregonator model. Selecting the time delay as bifurcation parameter, we obtain novel delay-independent bifurcation conditions that guarantee the stability and the appearance of Hopf bifurcation for the fractional-order delayed Oregonator model. The study shows that time delay plays a vital role in controlling the stability and the appearance of Hopf bifurcation of the considered fractional-order delayed Oregonator model. In order to verify the rationality of theoretical results, computer simulations are carried out.