Belousov-Zhabotinsky Reaction Research Articles

Multiscale Approach for Tuning Communication among Chemical Oscillators Confined in Biomimetic Microcompartments.

ConspectusInspired by the biological world, new cross-border disciplines and technologies have emerged. Relevant examples include systems chemistry, which offers a bottom-up approach toward chemical complexity, and bio/chemical information and communication technology (bio/chemical ICT), which explores the conditions for propagating signals among individual microreactors separated by selectively permeable membranes. To fabricate specific arrays of microreactors, microfluidics has been demonstrated as an excellent method. In particular, droplet-based microfluidics is a powerful tool for encapsulating biological entities and chemical reagents in artificial microenvironments, mostly water-in-oil microdroplets. In these systems, the interfaces are liquid-liquid, and their physicochemical properties are key factors for tuning the coupling between molecular diffusion. Simple and double emulsions, where aqueous domains are in equilibrium with oil domains through boundary layers of amphiphilic molecules, are organized assemblies with high interfacial-area-to-volume ratios. These membranes can be engineered to obtain different surface charges, single- or multilayer stacking, and a variable degree of defects in molecular packing. Emulsions find application in many fields, including the food industry, pharmaceutics, and cosmetics. Furthermore, micro- and nanoemulsions can be used to model the propagation of chemical species through long distances, which is not only vital for cell signaling but also significant in molecular computing. Here we present in-depth research on the faceted world of solutions confined in restricted environments. In particular, we focused on the multiscale aspects of structure and dynamics from molecular to micro and macro levels. The Belousov-Zhabotinsky chemical reaction, known for its robustness and well-documented oscillatory behavior, was selected to represent a generic signal emitter/receiver confined within microenvironments separated by liquid-liquid interfaces. In this pulse generator, the temporal and spatial progressions are governed by periodic fluctuations in the concentration of chemical species, which act as activatory or inhibitory messengers over long distances. When organized into "colonies" or arrays, these micro-oscillators exhibit emergent dynamical behaviors at the population level. These behaviors can be finely tuned by manipulating the geometrical distribution of the oscillators and the properties of the interfaces at the nanoscale. By carefully selecting the membrane composition, it is possible to drive the system toward either in-phase, antiphase, or mixed synchronization regimes among individual oscillators, depending on messenger molecules. This relatively simple lab-scale model replicates some of the communication strategies commonly found in biological systems, particularly those based on the passive diffusion of chemical and electrical signals. It can help shed light on fundamental life processes and inspire new implementations in molecular computing and smart materials.

Coupled X-ray Absorption/UV-vis Monitoring of a Prototypical Oscillating Reaction.

Oscillating reactions are among the most intriguing phenomena in chemistry, but many questions on their mechanisms still remain unanswered, due to their intrinsic complexity and to the low sensitivity of the most common spectroscopic techniques toward the reaction brominated species. In this work, we investigate the cerium ion-catalyzed Belousov-Zhabotinsky (BZ) oscillating reaction by means of time-resolved X-ray absorption spectroscopy (XAS), in combination with UV-vis spectroscopy and unsupervised machine learning, multivariate curve resolution, and kinetic analyses. Altogether, we provide new insights into the collective oscillatory behavior of the key brominated species involved in the classical BZ reaction and measure previously unreported oscillations in their concentrations through Br K-edge XAS, while simultaneously tracking the oscillatory Ce4+-to-Ce3+ transformation by coupling XAS with UV-vis spectroscopy. Our work evidences the potential of the XAS technique to investigate the mechanisms of oscillatory chemical systems whose species are often not detectable with conventional experimental methods.

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.

Emergent Synchronous Volumetric Oscillation in Hierarchically Structured Self-Oscillating Gel Clusters.

Emergent properties accompanying synchronization among oscillators are vital characteristics in biological systems. Belousov-Zhabotinsky (BZ) oscillators are an artificial model to study the emergence and synchronization in life. This research represents a self-oscillating gel system with clusterable properties to experimentally examine synchronous and emergent properties at a fundamental hierarchical level. Incorporating acrylic acid (AAc) moieties within the gel network facilitates cluster formation through hydrogen bonding in an acidic BZ substrate solution. Upon clustering, both homogeneous and heterogeneous gel assemblies─ranging from double to quadruple clusters─exhibit increased and synchronized periods and amplitudes during the BZ reaction. Notably, in heterogeneous clusters, gel units with initially short periods and small volumetric amplitudes display a significant increase, aligning with the lonfger periods and larger amplitudes of other elements within the cluster, an emergent property. This research can pave the way for a better understanding of synchronous and emergent properties in biological oscillators such as cardiomyocytes.

Photosensitive Control and Network Synchronization of Chemical Oscillators.

The Belousov-Zhabotinsky (BZ) reaction has long been a paradigmatic system for studying chemical oscillations. Here, we experimentally studied the synchronization control within photochemically coupled star networks of BZ oscillators. Experiments were carried out in wells performed in soda-lime glass constructed using novel laser technologies. Utilizing the inherent oscillatory nature of the BZ reaction, we engineered a star network of oscillators interconnected through photochemical inhibitory coupling. Furthermore, the experimental setup presented here could be extrapolated to more complex network architectures with both excitatory and inhibitory couplings, contributing to the fundamental understanding of synchronization in complex systems.

The Formalism of Chemical Thermodynamics Applied to an Oscillatory Multistep Chemical System

The thermodynamic optimization of a process focuses on consumption, production, and efficient use of energy. The unsteady-state nature of batch reactor processing requires describing the set of processes’ dynamic behavior for energy optimization. This work aims to apply the formalism of chemical thermodynamics to a multistep chemical system in a batch reactor, aiming for a dynamic description of its evolution to the equilibrium state. As the system of study, we selected a mathematical model called the Oregonator, derived from the mechanism of the oscillating Belousov-Zhabotinsky reaction. In the methodology, we used the reaction quotient to evaluate the Gibbs function, the thermodynamic affinity, and the entropy generation as a function of the reaction extent. The results show that the overall reaction fulfills the thermodynamic fundamentals of chemical equilibrium, despite having a non-stoichiometric coefficient. However, the multistep coupled reaction system does not allow verifying compliance with the thermodynamic foundations of chemical equilibrium. We conclude that it is necessary to improve thermodynamic formalism to describe multistep chemical processes as a function of a global reaction extent variable. In this scenario, the entropy production rate emerges as a promising quantity.

Periodical alternation between precipitation and dissolution of camphor solid film on an ethanol solution.

Rhythmic behaviors are generally observed in nonlinear chemical reactions such as the Belousov-Zhabotinsky reaction and enzymatic reactions. Similarly, a simple phase change can also lead to rhythmic behavior. It has been reported previously that camphor solid films alternate between generation and disappearance on ethanol (EtOH) solution, and a phenomenological mechanism has been suggested for this. The evaporation of EtOH decreases the temperature on the surface of the solution via vaporization heat and induces precipitation in the camphor solid film. At this time, the film prevents evaporation, and thus, the surface temperature increases due to thermal diffusion from the atmosphere, resulting in dissolution of the solid film. To verify the previously suggested phenomenological mechanism, we controlled the evaporation rate of EtOH using a porous plastic cover. As a result, the period of oscillation increased with decreasing pore diameter, and finally, the oscillation did not occur without pore in the cover, where the camphor solid film was not observed. Additionally, a new mathematical model was proposed, and the numerical calculations agreed well with experimental observations. Linear stability and bifurcation analyses revealed the detailed mechanism of this phenomenon, which agreed well with the phenomenological explanation mentioned above.

On phase correspondence between chemical oscillations in liquid Belousov-Zhabotinsky mixture filling catalyst-containing matrix and resulted gel's chemomechanical oscillations

We investigated phases and phase differences between coupled mechanical and chemical self-oscillations running in two kinds of newly synthesised chemomechanical gels. Processing of experimental data was model-free and it was based on spectral and wavelet approaches of the theory of dynamical systems. It was applied to samples of different sizes and compositions (Ru- and Fe-based gels). It was revealed that the Ru-based gels demonstrate a faster mechanical response to the redox changes of the Ru-moiety coupled to the Belousov-Zhabotinsky chemical reaction than the Fe-based gels. This demonstrated a significant phase difference between the redox changes of the Fe-moiety and the mechanical oscillations. Special attention was paid to the phase-coupling features for averaged higher harmonics, which are significant due to the high degree of nonlinearity of the chemomechanical oscillatory process.

Harmonic resonance and entrainment of propagating chemical waves by external mechanical stimulation in BZ self-oscillating hydrogels

Smart polymer materials that are nonliving yet exhibit complex "life-like" or biomimetic behaviors have been the focus of intensive research over the past decades, in the quest to broaden our understanding of how living systems function under nonequilibrium conditions. Identification of how chemical and mechanical coupling can generate resonance and entrainment with other cells or external environment is an important research question. We prepared Belousov-Zhabotinsky (BZ) self-oscillating hydrogels which convert chemical energy to mechanical oscillation. By cyclically applying external mechanical stimulation to the BZ hydrogels, we found that when the oscillation of a gel sample entered into harmonic resonance with the applied oscillation during stimulation, the system kept a "memory" of the resonant oscillation period and maintained it post stimulation, demonstrating an entrainment effect. More surprisingly, by systematically varying the cycle length of the external stimulation, we revealed the discrete nature of the stimulation-induced resonance and entrainment behaviors in chemical oscillations of BZ hydrogels, i.e., the hydrogels slow down their oscillation periods to the harmonics of the cycle length of the external mechanical stimulation. Our theoretical model calculations suggest the important roles of the delayed mechanical response caused by reactant diffusion and solvent migration in affecting the chemomechanical coupling in active hydrogels and consequently synchronizing their chemical oscillations with external mechanical oscillations.

Fractional Approach for Belousov-Zhabotinsky Reactions Model with Unified Technique

The Belousov-Zhabotinsky reaction model represents chemical oscillators that exhibit periodic vibrations as a result of complex physic-chemical phenomena. The non-linear behaviour exhibited by Belousov-Zhabotinsky model is the cause of Turing patterns, birth of spiral waves, rise of limit cycle attractors, and deterministic chaos in many chemical reaction processes. Due to these noteworthy characteristics, in this paper, we have analyzed mathematical Belousov-Zhabotinsky model by a novel numerical approach q-Homotopy analysis transformation method. To interpret new observations, we have incorporated Caputo fractional derivative in the model. The numerical result are presented graphically and concerning the absolute error of solutions. With the help of the homotopy parameter curve, we have projected the convergence region with reference to diverse values of fractional derivative. This work establishes that the projected numerical algorithm is a well-organized tool to analyze the multifaceted coupled partial differential equation representing Belousov-Zhabotinsky type reactions.

A comparative analysis of Noyes-Field model for the non-linear Belousov–Zhabotinsky reaction using two reliable techniques

Within the domain of nonlinear dynamics, the Belousov-Zhabotinsky reaction system has consistently captivated researchers, sustaining its position as a vibrant and dynamic area of exploration. As an enduring subject of study, the Belousov-Zhabotinsky system provides continuous opportunities to unravel the foundational tenets of nonlinear dynamics within intricate systems. In our quest to deepen comprehension of this complex system, we introduce an innovative methodology for addressing the time fractional Belousov-Zhabotinsky system. This novel approach leverages both the Natural Transform Iterative Method (NTIM) and the Optimal Homotopy Asymptotic Method (OHAM), aiming to contribute novel insights and methodologies to the ongoing discourse surrounding this intriguing and influential area of research. We obtained a series solution to test the accuracy of the suggested approach. The proposed technique has the advantage of requiring few calculations while producing high-precision results. To help you better understand, 2D and 3D graphical representations are provided to demonstrate the model's behavior and how changing the fractional order derivative in Caputo's sense and time affects the solutions.

A programmable hybrid digital chemical information processor based on the Belousov-Zhabotinsky reaction

The exponential growth of the power of modern digital computers is based upon the miniaturization of vast nanoscale arrays of electronic switches, but this will be eventually constrained by fabrication limits and power dissipation. Chemical processes have the potential to scale beyond these limits by performing computations through chemical reactions, yet the lack of well-defined programmability limits their scalability and performance. Here, we present a hybrid digitally programmable chemical array as a probabilistic computational machine that uses chemical oscillators using Belousov-Zhabotinsky reaction partitioned in interconnected cells as a computational substrate. This hybrid architecture performs efficient computation by distributing information between chemical and digital domains together with inbuilt error correction logic. The efficiency is gained by combining digital logic with probabilistic chemical logic based on nearest neighbour interactions and hysteresis effects. We demonstrated the computational capabilities of our hybrid processor by implementing one- and two-dimensional Chemical Cellular Automata demonstrating emergent dynamics of life-like entities called Chemits. Additionally, we demonstrate hybrid probabilistic logic as a viable logic for solving combinatorial optimization problems.

Active Pulsatile Gels: From a Chemical Microreactor to a Polymeric Actuator.

We report on a synthesis protocol, experimental characterization, and theoretical modeling of active pulsatile Belousov-Zhabotinsky (BZ) hydrogels. Our two-step synthesis technique allows independent optimization of the geometry, the chemical, and the mechanical properties of BZ gels. We identify the role of the surrounding medium chemistry and gel radius for the occurrence of BZ gel oscillations, quantified by the Damköhler number, which is the ratio of chemical reaction to diffusion rates. Tuning the BZ gel size to maximize its chemomechanical oscillation amplitude, we find that its oscillatory strain amplitude is limited by the time scale of gel swelling relative to the chemical oscillation period. Our experimental findings are in good agreement with a Vanag-Epstein model of BZ chemistry and a Tanaka Fillmore theory of gel swelling dynamics.

Collective chemomechanical oscillations in active hydrogels

We report on the collective response of an assembly of chemomechanical Belousov-Zhabotinsky (BZ) hydrogel beads. We first demonstrate that a single isolated spherical BZ hydrogel bead with a radius below a critical value does not oscillate, whereas an assembly of the same BZ hydrogel beads presents chemical oscillation. A BZ chemical model with an additional flux of chemicals out of the BZ hydrogel captures the experimentally observed transition from oxidized nonoscillating to oscillating BZ hydrogels and shows this transition is due to a flux of inhibitors out of the BZ hydrogel. The model also captures the role of neighboring BZ hydrogel beads in decreasing the critical size for an assembly of BZ hydrogel beads to oscillate. We finally leverage the quorum sensing behavior of the collective to trigger their chemomechanical oscillation and discuss how this collective effect can be used to enhance the oscillatory strain of these active BZ hydrogels. These findings could help guide the eventual fabrication of a swarm of autonomous, communicating, and motile hydrogels.

Photoinduced Nonlinear Dynamics of Strongly Correlated Systems with Spin Crossover: Autocatalytic Spin Transition

Nonlinear phenomena similar to the Belousov–Zhabotinsky reaction (autocatalytic oscillations of the population of high-spin and low-spin multielectron states of a transition metal ion) in open systems with spin crossover near bistability are considered. The conditions for possible experimental observation of autocatalytic oscillations of the magnetization in magnetically ordered systems with spin crossover are analyzed.

Bistable Wavefronts in the Delayed Belousov–Zhabotinsky Reaction

Bistable Wavefronts in the Delayed Belousov–Zhabotinsky Reaction

Neuromorphic Engineering in Wetware: Discriminating Acoustic Frequencies through Their Effects on Chemical Waves.

Some features of the human nervous system can be mimicked not only through software or hardware but also through liquid solutions of chemical systems maintained under out-of-equilibrium conditions. We describe the possibility of exploiting a thin layer of the Belousov-Zhabotinsky (BZ) reaction as a surrogate for the cochlea for sensing acoustic frequencies. Experiments and simulations demonstrate that, as in the human ear where the cochlea transduces the mechanical energy of the acoustic frequencies into the electrochemical energy of neural action potentials and the basilar membrane originates topographic representations of sounds, our bioinspired chemoacoustic system, based on the BZ reaction, gives rise to spatiotemporal patterns as the representation of distinct acoustic bands through transduction of mechanical energy into chemical energy. Acoustic frequencies in the range 10-2000 Hz are partitioned into seven distinct bands based on three attributes of the emerging spatiotemporal patterns: (1) the types and frequencies of the chemical waves, (2) their velocities, and (3) the Faraday waves' wavelengths.

Analytical and numerical computation of self-oscillating gels driven by the Belousov-Zhabotinsky reaction

Self-oscillating gel is a class of deformable polymers driven by Belousov-Zhabotinsky (BZ) reactions, which can form periodic deformations without any external stimuli, and are widely used in the research of micro actuators, AI sensors, drug release carriers or biomimetic materials. However, quantitative study on formation of the self-oscillating gel is limited especially from the perspective of energy conservation. This work adopts frequency domain analysis to the chemo-mechanical model, and the basic frequency is obtained to evaluate the maintenance energy of the deformable gel. For accurate computation, boundary value problem with unknown period is formulated; then, continuation algorithm based on technique of perturbation is performed to obtain the periodic trajectories with varying model parameters. The results could be implemented to design self-oscillating gels with prescribed periodicity.

Chemistry does general relativity: reaction-diffusion waves can model gravitational lensing

Gravitational lensing is a general relativistic (GR) phenomenon where a massive object redirects light, deflecting, magnifying, and sometimes multiplying its source. We use reaction-diffusion (RD) Belousov-Zhabotinsky (BZ) chemistry to study this astronomical effect in a table-top experiment. We experimentally observe BZ waves passing through non-planar, quasi-two-dimensional molds and reproduce the waveforms in computer simulations using planar RD waves propagating with variable diffusion. We tune the variable diffusion to match the Schwarzschild-coordinate light speed near a spherical mass so the RD propagation approximates Einstein’s famous light deflection relation. We discuss varying the diffusion or reaction rates with a gel matrix or with illumination, electric field, or temperature gradients.

A nonlinear continuum framework for constitutive modeling of active polymer gels

Chemo-mechanical transduction is one of the key mechanisms that has formed the basis for designing bio-inspired self-driven synthetic systems from soft materials. Polymer hydrogels that use Belousov–Zhabotinsky (BZ) reaction are a unique class of dynamical reaction–diffusion (RD) systems that can continuously transduce internal chemical energy, from the reaction, to produce sustained mechanical work. In particular, BZ gels represent a complex nonlinear chemo-mechanical system, wherein, the autocatalytic oscillatory BZ reaction drives the rhythmic mechanical deformations through polymer-solvent inter–diffusion. The objective of our work is to develop a standardized finite element (FE) framework for chemically driven active hydrogels that captures nonlinear elastic deformations with limited chain extensibility. The distinguishing feature of our approach is that, unlike other approaches, it combines reaction kinetics, solvent transport, elastodynamics of the polymeric network, and polymer-solvent friction under a unified FE framework. Moreover, we adapt our approach to a specific case of BZ gels and capture their swelling-deswelling characteristics. We first implement our FE framework in MATLAB that subsequently, forms the basis for constructing a three-dimensional user element subroutine (3D-UEL) in ABAQUS. Ultimately, through our simulations, we are able to capture all the essential features of BZ gels that includes chemically driven mechanical deformations. In addition, we also demonstrate that our 3D-UEL efficiently captures the chemo-mechanical response of “stent-shaped” BZ gels–a non-standard 3D geometry. In essence, our FE approach not only allows us to simulate BZ gels but also provides a template for other active, dynamical, RD-based systems, driven by chemo-mechanical transduction, irrespective of internal or external mechanisms.