Microfluidic Systems for the Belousov-Zhabotinsky Reaction

Brent T. Ginn, Niklas Manz and Oliver Steinbock Department of Chemistry and Biochemistry Florida State University, Tallahassee FL 32306-4390
We present results on reaction-diffusion systems in micro-patterned arrays. The arrays are fabricated using soft lithography and poly(dimethylsiloxane) as the matrix material. Each micro-reactor contains a minute volume of Belousov-Zhabotinsky solution. Spiral waves are observed for various concentrations and show tip dynamics that are strongly influenced by the micro-reactor geometry.
The Belousov-Zhabotinsky (BZ) Reaction and Microfluidic Systems The significance of this reaction lies in its model character for the study of temporal and spatio-temporal self-organization. The reaction exhibits for example oscillations and traveling waves as a result of its nonlinear dynamics. Here, the classic organic substrate (malonic acid) is replaced by 1,4cyclohexanedione (CHD). The implementation of microfluidic systems for studying the BZ reaction offers some very promising techniques. Microfluidic systems allow for the BZ reaction to easily be studied in microliter and possibly even nanoliter volumes. They also allow for study in pseudo one and two dimensions. Another valuable result of using these systems is that complex arrays may be miniaturized to micrometer dimensions for which chemical waves may complexly traverse. We discuss the process by which to create these microfluidic devices and the preparation of the BZ reaction. Also presented are data from experiments preformed in microfluidic systems as well as a discussion of observed reaction dynamics. A B C
Figure 1. Oxidation wave traveling through a BZ system in a patterned micro-reactor. The channel has a height of 80 m and a width of 50 m. The circular portion of the reactor has a diameter of 1 mm and the length of the reference bar (A) is 200 m. Initial BZ concentrations are [H2SO4] = 1.50 M, [CHD] = 0.15 M, [NaBrO3] = 0.10 M, [ferroin] = 3.1 mM. The snapshots are separated by t = 10 s.

Conclusion We have shown the usefulness of implementing soft lithography to miniaturize reaction arrays for study of the BZ reaction. Moreover, we observe interesting behavior of spiral waves in a grid-style micro-reactor. Spiral waves are observed to rotate rigidly around one obstacle (Figure 4) or a group of four obstacles (Figure 5). Analysis of spirals pinned to four obstacles reveals the spiral cores at the intersections of the BZ tracks (Figure 8A). The coordinate positions reveal times of propagation failures as excitation waves, resulting from a branching effect, reach the spiral core (Figure 8B). Meandering spiral waves exhibit interesting reaction dynamics in the grid-style microreactor. Analysis of the spiral tip trajectory in meandering concentration ranges (Figure 10A, D) reveals a complexity similar to that of a standard 2D system (Figure 9A); however, the tip trajectory is obviously influenced by the geometry of the reaction array. These complex trajectories are formed as a result of propagation failures during one cycle around the path (Figure 10B, E). References B. T. Ginn, B. Steinbock, M. Kahveci, and O. Steinbock "Microfluidic Systems for the Belousov-Zhabotinsky Reaction" submitted N. Manz, B. T. Ginn, and O. Steinbock, "Meandering Spiral Waves in the 1,4Cyclohexanedione Belousov-Zhabotinsky System Catalyzed by Fe[batho(SO3)2]34-/3-" submitted B. T. Ginn and O. Steinbock, "Polymer Surface Modification Using Microwave Oven Generated Plasma" in press (Langmuir) J. C. McDonald, D. C. Duffy, J. R. Anderson, D. T. Chiu, H. Wu, O. J. A. Schueller, G. M. Whitesides, Electrophoresis 2000, 21, 27-40

Figure 4. Motion of a single, clockwise rotating, spiral wave in a grid-style micro-reactor. The images (A-H) are separated by t = 20 s and have an area of 55 mm2. The spiral tip travels around a single PDMS obstacle, outlined in image (A). Initial BZ concentrations are [H2SO4] = 0.50 M, [CHD] = 0.15 M, [NaBrO3] = 0.10 M, [Fe[batho(SO3)2]34-] = 3.1 mM.

Figure 5. Evolution of a pair of rotating spiral waves in a grid-style micro-reactor. The images (A-H) are separated by t = 30 s and have an area of 55 mm2. The spiral tips travel around a group of four PDMS obstacles, outlined in image (A). Initial BZ concentrations are [H2SO4] = 0.50 M, [CHD] = 0.15 M, [NaBrO3] = 0.10 M, [Fe[batho(SO3)2]34-] = 3.1 mM. Figure 6. Schematic drawing of a spiral tip pathway around a group of four obstacles. Data are obtained by marking the position of the inner wave front A B C D E F G H (blue arrow). As a result of a branching effect at the intersections, the tip is noted to travel toward the center of the group (B, D, F, H). As the wave encounters the core at this intersection, a propagation failure results (marked by an ' in B, D, F, H). This propagation failure results in discontinuities of the tip trajectory. Figure 7. Spiral wave in a gridstyle BZ micro-reactor. The three-dimensional time-space plot is obtained from data shown in Figure 4, and highlights the motion of the clockwise rotating spiral tip. Time evolves along the vertical axis in upward direction spanning 270 s. The spiral tip is pinned to a single poly(dimethylsiloxane) obstacle. Initial BZ concentrations are [H2SO4] = 0.50 M, [CHD] = 0.15 M, [NaBrO3] = 0.10 M, [Fe[batho(SO3)2]34-] = 3.1 mM. The image area is 22 mm2. Figure 8. B A Analysis of data shown in Figure 5 revealing two spiral cores (A, see arrows) at the intersections of BZ tracks. For each pixel, the image data represents the maximum gray level detected for two rotational periods (300 s). The brightest regions correspond to the PDMS obstacles, whereas the spiral cores are small dark areas that do not undergo oxidation at any given time. The x-shaped appearance of the cores reflects repeated propagation failures of secondary spiral tips at the central intersections. Position of the most inwardly traveling wave front of the spiral as a function of time (B). The discontinuities reveal times at which propagation failures occur.

Wafer

A
Resist

Mask

Figure 2. Schematic drawing of master production by soft lithography (A-D) and device fabrication (E-H). A single side polished silicon wafer (A) is coated with SU-8 2100 resist and pre-baked (B). The photo mask is applied to the wafer, exposed to light, and then post-baked (C). The sample is developed and silanized (D). Unpolymerized PDMS is poured over the master (E). After polymerization, Glass the PDMS is peeled from the master (F). The device is cleaned, exposed Solution to air plasma and sealed to glass (G). In the last step, BZ solution is filled into the micro-reactor (H). Figure 3. Profilometric scan of a 22 mm2 area of a grid-style PDMS device before sealing. This device is the basis for all experiments presented.

PDMS

Figure 9. Example of a meandering pattern in a standard 2 dimension reaction layer (Manz, Ginn and Steinbock). The pattern formed by the trajectory of the spiral tip can be fit with a hypocycle (A). The x and y-positions vary in a sinusoidal fashion (B), a result of their orbital paths.

Figure 10. Complex spiral tip trajectories formed by meandering concentration ranges. Spatial plots depict the overall path of the spiral tip (A, D). The image area is 55 mm2. These complex trajectories are formed as a result of propagation failures during one cycle around the path (B, E, see arrows). Position of the most inwardly traveling wave front of the spiral as a function of time (C, F). The discontinuities reveal times at which propagation failures occur. Initial BZ concentrations are [H2SO4] = 0.09 M, [CHD] = 0.04 (AC) and 0.06 M (D-F), [NaBrO3] = 0.15 (A-C) and 0.20 M (D-F), [Fe[batho(SO3)2]34-] = 0.5 mM.