Belousov-Zhabotinsky Reaction Research Articles

Membrane Structure Drives Synchronization Patterns in Arrays of Diffusively Coupled Self-Oscillating Droplets.

Networks of diffusively coupled inorganic oscillators, confined in nano- and microcompartments, are effective for predicting and understanding the global dynamics of those systems where the diffusion of activatory or inhibitory signals regulates the communication among different individuals. By taking advantage of a microfluidic device, we study the dynamics of arrays of diffusively coupled Belousov-Zhabotinsky (BZ) oscillators encapsulated in water-in-oil single emulsions. New synchronization patterns are induced and controlled by modulating the structural and chemical properties of the phospholipid-based biomimetic membranes via the introduction of specific dopants. Doping molecules do not alter the membrane basic backbone, but modify the lamellarity (and, in turn, the permeability) or interact chemically with the reaction intermediates. A transition from two-period clusters showing 1:2 period-locking to one-period antiphase synchronization is observed by decreasing the membrane lamellarity. An unsynchronized scenario is found when the dopant is able to interfere with chemical communication by reacting with the chemical messengers.

The Behavior of BZ Reaction in Small Space with Liquid Marble

The Behavior of BZ Reaction in Small Space with Liquid Marble

Fabrication of Self-Oscillating Micelles with a Built-In Oxidizing Agent.

Various biological behaviors are fueled by "respiration", which is an example of catabolism. So far, we have reported various self-oscillating soft materials exhibiting bioinspired dynamic movements. These autonomous polymer systems are driven by the Belousov-Zhabotinsky (BZ) reaction, which is analogous to the tricarboxylic acid (TCA) cycle that is an integral part of respiration. However, in the BZ reaction, the external addition of an oxidizing agent is necessary to initiate the oxidation process, which is realized by intracellular moieties such as ubiquinone in living systems. Herein, we realized self-oscillating micelles that are driven without the external addition of an oxidizing agent. This was achieved by embedding the oxidizing source into the structure of the self-oscillating AB diblock copolymers. This strategy introduces a new function equivalent to intracellular oxidizing moieties, and is useful for the design of completely autonomous bioinspired materials.

Fabrication of Self‐Oscillating Micelles with a Built‐In Oxidizing Agent

AbstractVarious biological behaviors are fueled by “respiration”, which is an example of catabolism. So far, we have reported various self‐oscillating soft materials exhibiting bioinspired dynamic movements. These autonomous polymer systems are driven by the Belousov–Zhabotinsky (BZ) reaction, which is analogous to the tricarboxylic acid (TCA) cycle that is an integral part of respiration. However, in the BZ reaction, the external addition of an oxidizing agent is necessary to initiate the oxidation process, which is realized by intracellular moieties such as ubiquinone in living systems. Herein, we realized self‐oscillating micelles that are driven without the external addition of an oxidizing agent. This was achieved by embedding the oxidizing source into the structure of the self‐oscillating AB diblock copolymers. This strategy introduces a new function equivalent to intracellular oxidizing moieties, and is useful for the design of completely autonomous bioinspired materials.

Fabrication of New Belousov-Zhabotinsky Micro-Oscillators on the Basis of Silica Gel Beads.

We have fabricated and examined silica gel beads loaded with a catalyst of the Belousov-Zhabotinsky (BZ) reaction, tris(2,2'-bipyridyl)ruthenium(II) chloride, Ru(bpy)3Cl2, the BZ beads. The abilities of silica gel and the widely used ion-exchange resin (Dowex 50WX2) BZ beads to oscillate in a catalyst-free BZ solution are compared. The period of the BZ oscillations increases with an increase in the diameter (40-250 μm) of both types of the BZ beads. The ability of the ion-exchange resin beads to hold catalyst molecules significantly decreases with a decrease in pH, while this value is less dependent on pH for the silica gel BZ beads. The diffusive coupling of two BZ beads separated by either aqueous or oil gaps is studied as well. For the aqueous gap less than 100 μm, the BZ beads of both types demonstrate in-phase synchronization. For the oil phase, the Dowex BZ beads are unable to oscillate for a long enough time and therefore cannot be synchronized, while the silica gel BZ beads are able to oscillate for several hours and demonstrate anti-phase synchronization for gaps less than 40 μm.

Turbulent pattern in the 1,4-cyclohexanedione Belousov-Zhabotinsky reaction.

Chemical turbulence was observed experimentally in the 1,4-cyclohexanedione Belousov-Zhabotinsky (CHD-BZ) reaction in a double layer consisting of a catalyst-loaded gel and uncatalyzed liquid on a Petri dish. The chemical patterns in the CHD-BZ reaction occur spontaneously in various forms as follows: the initial, regular, transient, and turbulent patterns, subsequently. These four patterns are characterized by using the two-dimensional Fourier transform (2D-FT). Mechanism of the onset of the turbulence in the CHD-BZ reaction is proposed. Turbulence in the CHD-BZ reaction is reproducible under a well defined protocol and it exists for a period of time of about 50 minutes, which is sufficiently long to offer a good opportunity to study and control the turbulence in the future. Two models of the BZ reaction were used to simulate the spiral breakup. Both are capable of producing spiral turbulence from initially regular patterns in each layer and reflect certain features of dynamics observed in experiments.

Size- and position-dependent bifurcations of chemical microoscillators in confined geometries.

The present theoretical study deals with microparticles (beads) that contain an immobilized Belousov-Zhabotinsky (BZ) reaction catalyst. In the theoretical experiment, a BZ bead is immersed in a small water droplet that contains all of the BZ reaction reagents but no catalyst. Such heterogeneous reaction-diffusion BZ systems with the same BZ reactant concentrations demonstrate various dynamic modes, including steady state and low-amplitude, high-amplitude, and mixed-mode oscillations (MMOs). The emergence of such dynamics depends on the sizes of the bead and water droplet, as well as on the location of the bead inside the droplet. MMO emergence is explained by time-delayed positive feedback in combination with a canard phenomenon. If two identical BZ beads are immersed in the same droplet, many different dynamic modes including chaos are observed.

Designing multifunctional gels with electrical conductivity, mechanical toughness and self-oscillating performance

Self-oscillating polymer gels driven by the Belousov–Zhabotinsky (BZ) oscillating chemical reaction are a new class of functional gels that have potential applications in autonomously functioning membranes and as artificial muscle actuators.

Experimental verification of an opto-chemical "neurocomputer".

A theoretically predicted hierarchical network of pulse coupled chemical micro-oscillators and excitable micro-cells that we call a chemical "neurocomputer" (CN) or even a chemical "brain" is tested experimentally using the Belousov-Zhabotinsky reaction. The CN consists of five functional units: (1) a central pattern generator (CPG), (2) an antenna, (3) a reader for the CPG, (4) a reader for the antenna unit, and (5) a decision making (DM) unit. A hybrid CN, in which such chemical units as readers and DM units are replaced by electronic units, is tested as well. All these variations of the CN respond intelligently to external signals, since they perform an automatic transition from a current to a new dynamic mode of the CPG, which is similar to the antenna dynamic mode that in turn is induced by external signals. In other words, we show for the first time that a network of pulse coupled chemical micro-oscillators is capable of intelligent adaptive behavior.

BASIC CONCEPTS OF SELF-ORGANIZED PHENOMENA IN CHEMICAL SYSTEMS

We present the main concepts of nonlinear dynamics and thermodynamics of irreversible processes to introduce chemistry students to the topic of self-organized phenomena. This task is performed by theoretically describing the emergence of self-sustained oscillations, waves, and stationary patterns/Turing patterns in the Belousov-Zhabotinsky (BZ) reaction, through the Oregonator model. We carefully developed such a description, which resulted in long algebraic deductions and rich supplementary material. Considering that, we encourage the use of this material in undergraduate and graduate advanced physical chemistry classes.

An Alternative Spectrophotometric Determination of Carbaryl Insecticide Residues in Water Samples Using the Cerium-Catalyzed Belousov-Zhabotinsky Oscillating Reaction

An alternative approach for carbaryl determination based on the change in the oscillation period of the Belousov-Zhabotinsky (BZ) reaction under the addition of carbaryl is demonstrated. The oscillations were observed by spectrophotometric measurement at 320 nm, corresponding to the maximum absorption wavelength of cerium(IV) catalyst. The oscillation periods increase with the carbaryl concentrations, which can be discussed based on the Field-Koros-Noyes (FKN) mechanism. The increase of oscillation periods is proportional to the concentration of carbaryl in the range of 0.1-200 mg L-1 with the regression coefficient of 0.9938. The limits of detection and quantification were 0.044 and 0.147 mg L-1, respectively. The precisions in terms of intra-day and inter-day measurements were efficient with relative standard deviation (RSD) lower than 2.1%. Accuracy of carbaryl in different water samples was obtained with high recoveries in the range of 94-106% and also comparable to the results of high performance liquid chromatography (HPLC) analysis. The proposed method is precise, cost-effective and can be alternatively employed for the screening and determination of carbaryl residues in water samples.

Efficiency range of the Belousov-Zhabotinsky reaction to induce the self-organization of transient bonds in metallo-supramolecular polymeric systems.

The periodic change of the oxidation state of the metal catalyst in the oscillating Belousov-Zhabotinsky (BZ) reaction has been reported to establish a periodic organization of metallo-supramolecular bonds in polymeric systems, which results in autonomous viscosity oscillations. To appraise the possible extent of quantitative control on the viscosity oscillation features, we assess how the kinetics of the BZ reaction affects the periodic self-organization of the metal-ligand coordination, and vice versa. Our model system includes mono-, bis-, and tetra-functional polyethyleneglycol (PEG) precursors end grafted with terpyridine ligands that are complexed with ruthenium ions, which oscillate between Ru2+ and Ru3+ oxidation states in the BZ reaction medium. The control parameters are divided into microscopic factors, which are responsible for the local reaction rate, and mesoscopic factors, which are responsible for the spatial distribution of the concentration patterns. The reactant concentrations are found to nonlinearly control the amplitude and periods of reduction and oxidation phases, independent of the precursor functionalization degree. An increased medium viscosity, and therewith cease of mixing, accelerates the reaction rate by localization of the reaction phases, even though the diffusion of reaction intermediates causes a periodic chemical wave with distinct harmonics. Time-course viscosity measurements of the tetra-arm precursors in the BZ medium demonstrate an initial overshoot followed by minor oscillations around a plateau that is significantly lower than the viscosity of an equivalent fully associated network. Apparently, the slow association kinetics of Ru2+-bis(terpyridine) limits the frequency and the extent of self-organization, and this way, avoids full establishment of the expected viscosity oscillation.

Microfluidic compartmentalization of diffusively coupled oscillators in multisomes induces a novel synchronization scenario.

Stable cell-like multisomes encapsulating the chemical oscillator Belousov-Zhabotinsky were engineered and organized in a linear network of diffusively-coupled chemical oscillators by using microfluidics. The multi-compartmentalization and the spatial configuration resulted in a new global synchronization scenario. After an initial induction interval, all the oscillators started to pulsate in phase with a halved period with respect to the natural one.

0D-2D heterostructures as nanocatalysts for self-oscillating reactions: an investigation into chemical kinetics.

Self-oscillating chemical reactions are dynamical reaction-diffusion systems that show immense potential in the design of synthetic soft materials with biomimetic functionalities. The Belousov-Zhabotinsky (BZ) reaction is one such reaction, where the periodic change in the redox state of the metal ion catalyst drives the rhythmic chemical oscillations. Inspired by the exceptional properties of graphene, specifically its catalytic activity for redox reactions, we investigate the effect of graphene-based nanocomposites on the dynamics of the BZ reaction. In particular, we synthesized catalytic mats by decorating ceria nanoparticles (CeNPs) on graphene-based nanosheets, thereby creating 0D-2D heterostructures and subsequently, incorporate these catalytic mats into the BZ reaction. Our investigations reveal that CeNP decorated nanocomposites significantly enhance the oscillating frequency of the BZ reaction, not only compared to the traditional solution-based catalysts but also compared to the bare graphene-based nanosheets. From our experiments at various temperatures and concentrations, together with modelling and simulations, we determine the apparent rate constant for different CeNP decorated graphene nanocomposites. Ultimately, we determine the apparent rate and estimate various kinetic parameters, including activation energy and reaction order. In short, we demonstrate that CeNP decorated nanomats are excellent catalysts and elucidate that the kinetics of the BZ reaction can be simulated using the Oregonator model with our kinetic parameters. We envisage that our findings can be utilized to harness multiscale interactions to design a variety of multifunctional stimuli responsive materials.

Positivity-Preserving Numerical Methods for Belousov-Zhabotinsky Reaction

The existence of positive solutions to the system of ordinary differential equations related to the Belousov-Zhabotinsky reaction is established. The key idea is to use a new successive approximation of solutions, ensuring its positivity. To obtain the positivity and invariant region for numerical solutions, the system is discretized as difference equations of explicit form, employing operator splitting methods with linear stability conditions. Algorithm to solve the alternate solution is given.

Threaded Rings that Swim in Excitable Media.

Cardiac tissue and the Belousov-Zhabotinsky reaction provide two notable examples of excitable media that support scroll waves, in which a filament core is the source of spiral waves of excitation. Here we consider a novel topological configuration in which a closed filament loop, known as a scroll ring, is threaded by a pair of counterrotating filaments that are perpendicular to the plane of the ring and end on the boundary of a thin medium. We simulate the dynamics of this threaded ring (thring) in the photosensitive Belousov-Zhabotinsky excitable medium, using the modified Oregonator reaction-diffusion equations. These computations reveal that the threading topology induces an exotic motion in which the thring swims in the plane of the ring. We propose a light templating protocol to create a thring in the photosensitive Belousov-Zhabotinsky medium and provide experimental confirmation that this protocol indeed yields a thring.

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.

Visual chemo-chronometric assay for quantifying ethanol in alcoholic drinks by the colorimetric Belousov-Zhabotinsky oscillator

A simple chemo-chronometric method utilizing the Belousov-Zhabotinsky (BZ) oscillating reaction for the efficient detection of ethanol in alcoholic beverages has been developed. This visual detecting strategy only required a smartphone, without implemented instrumental detection systems, to video a unique colorimetric alternating (red-to-blue) feature of the BZ solution system containing 0.50 M bromate, 0.12 M malonic acid, 0.03 M bromide, 0.10 M sulfuric acid, and 0.2 mM ferroin under the perturbation of ethanol. The RGB intensity signals, termed the colorimetric oscillating signals (COS), could be drawn from recorded files through the image processing. We found from the COS characteristics that the oscillation period was inversely proportional to the ethanol levels as a consequence of its reaction with bromate in the studied system. Based on the established calibration, the ethanol content was effectively evaluated with good precision (<2.8% RSD). Also, the assay was successful with 5% error for the quantification of ethanol in commercial drink samples, signifying its accuracy and potential applicability.

Flow chemistry controls self-assembly and cargo in Belousov-Zhabotinsky driven polymerization-induced self-assembly

Amphiphilic block-copolymer vesicles are increasingly used for medical and chemical applications, and a novel method for their transient self-assembly orchestrated by periodically generated radicals during the oscillatory Belousov-Zhabotinsky (BZ) reaction was recently developed. Here we report how combining this one pot polymerization-induced self-assembly (PISA) method with a continuously stirred tank reactor (CSTR) strategy allows for continuous and reproducible control of both the PISA process and the chemical features (e.g. the radical generation and oscillation) of the entrapped cargo. By appropriately tuning the residence time (τ), target degree of polymerization (DP) and the BZ reactants, intermediate self-assembly structures are also obtained (micelles, worms and nano-sized vesicles). Simultaneously, the chemical properties of the cargo at encapsulation are known and tunable, a key advantage over batch operation. Finally, we also show that BZ-driven polymerization in CSTR additionally supports more non-periodic dynamics such as bursting.

Potentiometric Determination of Paracetamol in Pharmaceutical Formulations by the Analyte Pulse Perturbation Technique using Belousov–Zhabotinskii Oscillating chemical Reaction

The present work proposes the development of an analytical procedure for paracetamol determination in pharmaceutical formulations using a system of continuous flow analysis associated with potentiometric detection allowing the study of the Belousov–Zhabotinskii (BZ) oscillating reaction. This method is based on paracetamol determination using the disturbance in the oscillation pattern of the BZ reaction promoted by this substance. The analytical curve showed the detection and quantification limits of 4 × 10–6 and 1.2 × 10–5 M, respectively. The relative standard deviation (n = 6) of the standard solution with paracetamol concentration of 6 mM was 2.3%. The analysis of real samples by the proposed and official methods (spectrophotometry/UV) showed similar results.