Periodic perturbation of chemical oscillators: entrainment and induced synchronization.

It is well known that a large number of catalyst-carrying beads immersed in an oscillatory chemical medium (Belousov-Zhabotinsky reaction) display collective oscillatory behavior. Using a light sensitive version of BZ, we show that this collective behavior can be entrained to an external light source with an oscillatory intensity. Thus, the emerging collective behavior can be controlled by an external perturbation.

Self-organized tubular structures as platforms for quantum dots.

The combination of top-down and bottom-up approaches offers great opportunities for the production of complex materials and devices. We demonstrate this approach by incorporating luminescent CdSe-ZnS nanoparticles into macroscopic tube structures that form as the result of externally controlled self-organization. The 1-2 mm wide hollow tubes consist of silica-supported zinc oxide/hydroxide and are formed by controlled injection of aqueous zinc sulfate into a sodium silicate solution. The primary growth region at the top of the tube is pinned to a robotic arm that moves upward at constant speed. Dispersed within the injected zinc solution are 3.4 nm CdSe-ZnS quantum dots (QDs) capped by DHLA-PEG-OCH3 ligands. Fluorescence measurements of the washed and dried tubes reveal the presence of trapped QDs at an estimated number density of 10(10) QDs per millimeter of tube length. The successful inclusion of the nanoparticles is further supported by electron microscopy and energy dispersive X-ray spectroscopy, with the latter suggesting a nearly homogeneous QD distribution across the tube wall. Exposure of the samples to copper sulfate solution induces quenching of about 90% of the tubes' fluorescence intensity. This quenching shows that the large majority of the QDs is chemically accessible within the microporous, about 15-µm-wide tube wall. We suggest possible applications of such QD-hosting tube systems as convenient sensors in microfluidic and related applications.

Postsynthetic processing of copper hydroxide-silica tubes.

Using reaction conditions far from equilibrium, we produce hollow tubes of silica-supported Cu(OH)2. The samples are then processed postsynthetically without compromising the macroscopic tubular structure. We specifically induce an amorphous-crystalline transition and demonstrate the sequential conversion of Cu(OH)2 to CuO, Cu2O, and metallic copper using thermal treatment and wet chemistry.

Nonequilibrium synthesis of silica-supported magnetite tubes and mechanical control of their magnetic properties.

Materials synthesis far from thermodynamic equilibrium can yield hierarchical order that spans from molecular to macroscopic length scales. Here we report the nonequilibrium formation of millimeter-scale iron oxide-silica tubes in experiments that tightly control the tube radius and growth speed. The experiments involve the hydrodynamic injection of an iron (II,III) solution into a large volume of solution containing sodium silicate and ammonium hydroxide. The forming tubes are pinned to a motorized glass rod that moves at a predetermined speed. X-ray diffraction and electron microscopy, as well as Raman and Mössbauer spectroscopy, reveal magnetite nanoparticles in the range of 5-15 nm. Optical data suggest that the magnetite particles follow first-order nucleation-growth kinetics. The hollow tubes exhibit superparamagnetic behavior at room temperature, with a transition to a blocked state at T(B) = 95 K for an applied field of 200 Oe. Heat capacity measurements yield evidence for the Verwey transition at 20 K. Finally, we show a remarkable dependence of the tubes' magnetic properties on the speed of the pinning rod and the injection rate employed during synthesis.

Tubular precipitation structures: materials synthesis under non-equilibrium conditions.

Inorganic precipitation reactions are known to self-organize a variety of macroscopic structures, including hollow tubes. We discuss recent advances in this field with an emphasis on experiments similar to 'silica gardens'. These reactions involve metal salts and sodium silicate solution. Reactions triggered from reagent-loaded microbeads can produce tubes with inner radii of down to 3 µm. Distinct wall morphologies are reported. For pump-driven injection, three qualitatively different growth regimes exist. In one of these regimes, tubes assemble around a buoyant jet of reactant solution, which allows the quantitative prediction of the tube radius. Additional topics include relaxation oscillations and the templating of tube growth with pinned gas bubble and mechanical devices. The tube materials and their nano-to-micro architectures are discussed for the cases of silica/Cu(OH)(2) and silica/Zn(OH)(2)/ZnO tubes. The latter case shows photocatalytic activity and photoluminescence.

Propagating fronts in thin tubes: concentration, electric, and pH effects in a two-dimensional precipitation pulse system.

In this paper, we studied the dynamics of a CaCO3 precipitate deposition pulse in a thin, long tube connecting two reservoir sinks of coprecipitates. The pulse profile, as well as the time t(c) and distance x(c) of the first appearance of precipitate, is studied as a function of the initial concentration of CO(3)(2-) in the right reservoir, [CO(3)(2-)](0), and later as a function of an applied external electric field at different voltages. The time variations of the pulse location and the pH at the center of the tube are determined. The distance from the calcium chloride sink (x) at any fixed time decreases as [CO(3)(2-)](0) increases. The time evolution of the front location exhibits a crossover between an early time regime and a late time regime. The pH-time curve shows a marked resemblance with a sigmoid shape. At any time, the pH consistently increases with [CO(3)(2-)](0). In the presence of a constant electric field applied across the tube (fixed voltage), t(c) decreased with the field strength, whereas x(c) exhibited a correlated increase. Irregularities in the variation of distance with the applied voltage (at a fixed time) were noted. The pH experiences a slight increase with the applied voltage. The pulse width exhibits a nonlinear time dependence, of the form w = a + bt(1/6). The shape of the deposition pulse deviates from a Gaussian distribution. This study is of special interest in the experimental simulation and modeling of precipitate deposition and potential clogging in microcapillary channels.