C. Patrick Collier

Two-Dimensional Molecular Electronics Circuits

Addressing an array of bistable [2]rotaxanes through a two-dimensional crossbar arrangement provides the device element of a current-driven molecular electronic circuit. The development of the [2]rotaxane switches through an iterative, evolutionary process is described. The arrangement reported here allows both memory and logic functions to use the same elements.

Delayed Frost Growth on Jumping-Drop Superhydrophobic Surfaces

Self-propelled jumping drops are continuously removed from a condensing superhydrophobic surface to enable a micrometric steady-state drop size. Here, we report that subcooled condensate on a chilled superhydrophobic surface are able to repeatedly jump off the surface before heterogeneous ice nucleation occurs. Frost still forms on the superhydrophobic surface due to ice nucleation at neighboring edge defects, which eventually spreads over the entire surface via an interdrop frost wave. The growth of this interdrop frost front is shown to be up to 3 times slower on the superhydrophobic surface compared to a control hydrophobic surface, due to the jumping-drop effect dynamically minimizing the average drop size and surface coverage of the condensate. A simple scaling model is developed to relate the success and speed of interdrop ice bridging to the drop size distribution. While other reports of condensation frosting on superhydrophobic surfaces have focused exclusively on liquid-solid ice nucleation for isolated drops, these findings reveal that the growth of frost is an interdrop phenomenon that is strongly coupled to the wettability and drop size distribution of the surface. A jumping-drop superhydrophobic condenser minimized frost formation relative to a conventional dropwise condenser in two respects: preventing heterogeneous ice nucleation by continuously removing subcooled condensate, and delaying frost growth by limiting the success of interdrop ice bridge formation.

Dynamic defrosting on nanostructured superhydrophobic surfaces.

Water suspended on chilled superhydrophobic surfaces exhibits delayed freezing; however, the interdrop growth of frost through subcooled condensate forming on the surface seems unavoidable in humid environments. It is therefore of great practical importance to determine whether facile defrosting is possible on superhydrophobic surfaces. Here, we report that nanostructured superhydrophobic surfaces promote the growth of frost in a suspended Cassie state, enabling its dynamic removal upon partial melting at low tilt angles (<15°). The dynamic removal of the melting frost occurred in two stages: spontaneous dewetting followed by gravitational mobilization. This dynamic defrosting phenomenon is driven by the low contact angle hysteresis of the defrosted meltwater relative to frost on microstructured superhydrophobic surfaces, which forms in the impaled Wenzel state. Dynamic defrosting on nanostructured superhydrophobic surfaces minimizes the time, heat, and gravitational energy required to remove frost from the surface, and is of interest for a variety of systems in cold and humid environments.

Air-stable droplet interface bilayers on oil-infused surfaces

Significance By suspending a lipid bilayer in an aperture or between water droplets, single-molecule transport through membrane channels can be electrically detected. To date, all suspended bilayers have been confined to fluid reservoirs. This study demonstrates that droplet interface bilayers can be created in an ambient environment using noncoalescing water droplets on an oil-infused surface. Air-stable droplet interface bilayers are easy to manipulate and electrically characterize, and could potentially allow for the biosensing of airborne molecules. Droplet interface bilayers are versatile model membranes useful for synthetic biology and biosensing; however, to date they have always been confined to fluid reservoirs. Here, we demonstrate that when two or more water droplets collide on an oil-infused substrate, they exhibit noncoalescence due to the formation of a thin oil film that gets squeezed between the droplets from the bottom up. We show that when phospholipids are included in the water droplets, a stable droplet interface bilayer forms between the noncoalescing water droplets. As with traditional oil-submerged droplet interface bilayers, we were able to characterize ion channel transport by incorporating peptides into each droplet. Our findings reveal that droplet interface bilayers can function in ambient environments, which could potentially enable biosensing of airborne matter.

Controlling condensation and frost growth with chemical micropatterns

In-plane frost growth on chilled hydrophobic surfaces is an inter-droplet phenomenon, where frozen droplets harvest water from neighboring supercooled liquid droplets to grow ice bridges that propagate across the surface in a chain reaction. To date, no surface has been able to passively prevent the in-plane growth of ice bridges across the population of supercooled condensate. Here, we demonstrate that when the separation between adjacent nucleation sites for supercooled condensate is properly controlled with chemical micropatterns prior to freezing, inter-droplet ice bridging can be slowed and even halted entirely. Since the edge-to-edge separation between adjacent supercooled droplets decreases with growth time, deliberately triggering an early freezing event to minimize the size of nascent condensation was also necessary. These findings reveal that inter-droplet frost growth can be passively suppressed by designing surfaces to spatially control nucleation sites and by temporally controlling the onset of freezing events.

Self-propelled sweeping removal of dropwise condensate

Dropwise condensation can be enhanced by superhydrophobic surfaces on which the condensate drops spontaneously jump upon coalescence. However, the self-propelled jumping in prior reports is mostly perpendicular to the substrate. Here, we propose a substrate design with regularly spaced micropillars. Coalescence on the sidewalls of the micropillars leads to self-propelled jumping in a direction nearly orthogonal to the pillars and therefore parallel to the substrate. This in-plane motion in turn produces sweeping removal of multiple neighboring drops. The spontaneous sweeping mechanism may greatly enhance dropwise condensation in a self-sustained manner.

Asymmetric Wettability of Nanostructures Directs Leidenfrost Droplets

Leidenfrost phenomena on nano- and microstructured surfaces are of great importance for increasing control over heat transfer in high power density systems utilizing boiling phenomena. They also provide an elegant means to direct droplet motion in a variety of recently emerging fluidic systems. Here, we report the fabrication and characterization of tilted nanopillar arrays (TNPAs) that exhibit directional Leidenfrost water droplets under dynamic conditions, namely on impact with Weber numbers ≥40 at T ≥ 325 °C. The directionality for these droplets is opposite to the direction previously exhibited by macro- and microscale Leidenfrost ratchets where movement against the tilt of the ratchet was observed. The batch fabrication of the TNPAs was achieved by glancing-angle anisotropic reactive ion etching of a thermally dewet platinum mask, with mean pillar diameters of 100 nm and heights of 200-500 nm. In contrast to previously implemented macro- and microscopic Leidenfrost ratchets, our TNPAs induce no preferential directional movement of Leidenfrost droplets under conditions approaching steady-state film boiling, suggesting that the observed droplet directionality is not a result of the widely accepted mechanism of asymmetric vapor flow. Using high-speed imaging, phase diagrams were constructed for the boiling behavior upon impact for droplets falling onto TNPAs, straight nanopillar arrays, and smooth silicon surfaces. The asymmetric impact and directional trajectory of droplets was exclusive to the TNPAs for impacts corresponding to the transition boiling regime, linking asymmetric surface wettability to preferential directionality of dynamic Leidenfrost droplets on nanostructured surfaces.

Fast mixing and reaction initiation control of single-enzyme kinetics in confined volumes.

A device with femtoliter-scale chambers and controlled reaction initiation was developed for single-molecule enzymology. Initially separated substrate and enzyme streams were rapidly mixed in a microfluidic device and encapsulated in an array of individual microreactors, allowing for enzyme kinetics to be monitored with millisecond dead times and single-molecule sensitivity. Because the arrays of chambers were fabricated by micromolding in PDMS, the chambers were monodisperse in size, and the chamber volume could be systematically controlled. Microreactors could be purged and replenished with fresh reactants for consecutive rounds of observation. Repeated experiments with statistically identical initial conditions could be performed rapidly, with zero cross-talk between chambers in the array.

Monodisperse alginate microgel formation in a three-dimensional microfluidic droplet generator

Droplet based microfluidic systems provide an ideal platform for partitioning and manipulating aqueous samples for analysis. Identifying stable operating conditions under which droplets are generated is challenging yet crucial for real-world applications. A novel three-dimensional microfluidic platform that facilitates the consistent generation and gelation of alginate-calcium hydrogel microbeads for microbial encapsulation, over a broad range of input pressures, in the absence of surfactants is described. The unique three-dimensional design of the fluidic network utilizes a height difference at the junction between the aqueous sample injection and organic carrier channels to induce droplet formation via a surface tension enhanced self-shearing mechanism. Combined within a flow-focusing geometry, under constant pressure control, this arrangement facilitates predictable generation of droplets over a much broader range of operating conditions than that of conventional two-dimensional systems. The impact of operating pressures and geometry on droplet gelation, aqueous and organic material flow rates, microbead size, and bead generation frequency are described. The system presented provides a robust platform for encapsulating single microbes in complex mixtures into individual hydrogel beads, and provides the foundation for the development of a complete system for sorting and analyzing microbes at the single cell level.

Shear-driven redistribution of surfactant affects enzyme activity in well-mixed femtoliter droplets.

We developed a microfluidic platform for splitting well-mixed, femtoliter-volume droplets from larger water-in-oil plugs, where the sizes of the daughter droplets were not limited by channel width. These droplets were separated from mother plugs at a microfabricated T-junction, which enabled the study of how increased confinement affected enzyme kinetics in droplets 4-10 microm in diameter. Initial rates for enzyme catalysis in the mother plugs and the largest daughter drops were close to the average bulk rate, while the rates in smaller droplets decreased linearly with increasing surface to volume ratio. Rates in the smallest droplets decreased by a factor of 4 compared to the bulk rate. Traditional methods for detecting nonspecific adsorption at the water-oil interface were unable to detect evidence of enzyme adsorption, including pendant drop tensiometry, laser scanning confocal microscopy of drops containing labeled proteins in microemulsions, and epifluorescence microscopy of plugs and drops generated on-chip. We propose the slowing of enzyme reaction kinetics in the smaller droplets was the result of increased adsorption and inactivation of enzymes at the water-oil interface arising from transient interfacial shear stresses imparted on the daughter droplets as they split from the mother plugs and passed through the constricted opening of the T-junction. Such stresses are known to modulate the interfacial area and density of surfactant molecules that can passivate the interface. Bright field images of the splitting processes at the junction indicate that these stresses scaled with increasing surface to volume ratios of the droplets but were relatively insensitive to the average flow rate of plugs upstream of the junction.