Microfluidic fabrication of stable gas-filled microcapsules for acoustic contrast enhancement.

We introduce a facile approach for the production of gas-filled microcapsules designed to withstand high pressures. We exploit microfluidics to fabricate water-filled microcapsules that are then externally triggered to become gas-filled, thus making them more echogenic. In addition, the gas-filled microcapsules have a solid polymer shell making them resistant to pressure-induced buckling, which makes them more mechanically robust than traditional prestabilized microbubbles; this should increase the potential of their utility for acoustic imaging of porous media with high hydrostatic pressures such as oil reservoirs.

The design of wrinkled microcapsules for enhancement of release rate.

Thermally expandable microcapsules (TEMs) with wrinkled shells are prepared by one-step suspension polymerization, allowing for encapsulation and controlled release of cargos. Wrinkling results from concurrent crosslinking of shell copolymers and vaporization of volatile reagents along with density increase upon polymerization. Through control of the vapor pressure of the reagents and systematic variation of the suspension composition, microcapsules with different degrees of wrinkling are prepared, ranging from locally dimpled to highly crumpled morphologies. The corresponding increase of the surface-to-volume ratio results in increasing release rate of encapsulated oil red dye as a model cargo. As such, in addition to shell thickness and radius, the wrinkleness provides an effective control parameter for adjusting the release rate. The wrinkled microcapsules with a large surface-to-volume ratio may find applications in drug delivery, chemicals scavenging, and self-healing materials.

Programming temporal shapeshifting.

Shapeshifting enables a wide range of engineering and biomedical applications, but until now transformations have required external triggers. This prerequisite limits viability in closed or inert systems and puts forward the challenge of developing materials with intrinsically encoded shape evolution. Herein we demonstrate programmable shape-memory materials that perform a sequence of encoded actuations under constant environment conditions without using an external trigger. We employ dual network hydrogels: in the first network, covalent crosslinks are introduced for elastic energy storage, and in the second one, temporary hydrogen-bonds regulate the energy release rate. Through strain-induced and time-dependent reorganization of the reversible hydrogen-bonds, this dual network allows for encoding both the rate and pathway of shape transformations on timescales from seconds to hours. This generic mechanism for programming trigger-free shapeshifting opens new ways to design autonomous actuators, drug-release systems and active implants.