Fine tuning of pattern selection in the cadmium-hydroxide-system.

Controlling self-organization in precipitation reactions has received growing attention in the efforts of engineering highly ordered spatial structures. Experiments have been successful in regulating the band patterns of the Liesegang phenomenon on various scales. Herein, we show that by adjusting the composition of the hydrogel medium, we can switch the final pattern between the classical band structure and the rare precipitate spots with hexagonal symmetry.

Periodic Nucleation of Calcium Phosphate in a Stirred Biocatalytic Reaction.

Highly ordered superstructures composed of inorganic nanoparticles appear in natural and synthetic systems, however the mechanisms of non-equilibrium self-organization that may be involved are still poorly understood. Herein, we performed a kinetic investigation of the precipitation of calcium phosphate using a process widely found in microorganisms: the hydrolysis of urea by enzyme urease. With high initial ratio of calcium ion to phosphate, periodic precipitation was obtained accompanied by pH oscillations in a well-stirred, closed reactor.

Osmotic contribution to the flow-driven tube formation of copper-phosphate and copper-silicate chemical gardens.

We have produced hollow copper-containing precipitate tubes using a flow-injection technique, and characterized their linear and volume growth. It is shown that the ratio of the volume increase rate to that of pumping is constant independent of the chemical composition. It is also found that osmosis significantly contributes to the tube growth, since the inward flux of chemical species dominates during the precipitate pattern formation.

Flow-driven pattern formation in the calcium-oxalate system.

The precipitation reaction of calcium oxalate is studied experimentally in the presence of spatial gradients by controlled flow of calcium into oxalate solution. The density difference between the reactants leads to strong convection in the form of a gravity current that drives the spatiotemporal pattern formation. The phase diagram of the system is constructed, the evolving precipitate patterns are analyzed and quantitatively characterized by their diameters and the average height of the gravity flow.

Self-Assembly of Charged Nanoparticles by an Autocatalytic Reaction Front.

In this work we present that aggregation of charged and pH sensitive nanoparticles can be spatiotemporally controlled by an autonomous way using the chlorite-tetrathionate autocatalytic front, where the front regulates the electrostatic interaction between nanoparticles due to protonation of the capping (carboxylate-terminated) ligand. We found that the aggregation and sedimentation of nanoparticles in liquid phase with the effect of reversible binding of the autocatalyst (H(+)) play important roles in changing the front stability (mixing length) and the velocity of the front in both cases when the fronts propagate upward and downward. Calculation of interparticle interactions (electrostatic and van der Waals) with the measurement of front velocity revealed that the aggregation process occurs fast (within a few seconds) at the front position.