Hole-shell microparticles from controllably evolved double emulsions.

Polymeric core–shell microparticles with hollow interiors have great potential for use as microencapsulation systems for controlled load/release, active protection, and confined microreaction. Core–shell structures with solid shells provide effective encapsulation; however, transport of the encapsulated molecule through the shell is more difficult. Addition of holes to the shell can provide more versatility for the microparticles by facilitating mass transport through the shell based on the size or functional selectivity of the holes; this produces microparticles with porous shells for a myriad of uses including controlled capture of particles, controlled release of active molecules and small particles, and removal of pollutants. Additional uses for these microparticles can be achieved through finer control of the holes in the shell: for example, a single, defined hole can provide a very versatile structure for selectively capturing particles for classification and separation, or capturing cells for confined culture. Even more versatility can be obtained through control of the shape of the hollow core: for example, microparticles with a dimple-shaped core are useful for sizeselective capture of colloidal particles, whereas microparticles with a fishbowl-shaped core are more useful for loading objects such as cells and confining a microreaction. Finally, to make these structures fully functional, it is also desirable to control the interfacial properties of the core to enable precise interactions between encapsulated molecules and the solid shell. Colloidal-scale core–shell microparticles with a single hole in the shell are typically made with particle or emulsiontemplate methods: polymerization-induced buckling of silicon drops, freeze-drying solvent-swollen polymeric particles, self-assembly of phase-separated polymers, diffusion-induced escape of monomers or solvents from the microparticles during fabrication, selective polymerization of phase-separated drops, and other means to control the phase behavior of the templates. These microparticles provide excellent performance when sizes less than a few microns are required. By contrast, larger microparticles provide additional versatility when the size requirements are not constrained to very small particles. These microparticles are typically formed using emulsion drops as templates and have sizes of tens of micrometers or larger. Even finer control over the monodispersity of the microparticles is achieved using microfluidic techniques to produce the emulsion templates. The microparticle structure strongly depends on the configuration between the coredrop and shell-drop in the emulsion templates. With the shelldrop partially wetted on the core-drop, organic-biphasic Janus drops produce truncated-sphere-shaped microparticles. With completely wetted core–shell configurations, aqueousbiphasic drops and water-in-oil-in-water (W/O/W) double emulsions respectively produce bowl-shaped and fishbowlshaped microparticles. Surface modification of these microparticles was recently achieved by introducing functional nanoparticles such as SiO2 nanoparticles into the organic phase of the emulsion templates. Complete versatility of the microparticles requires accurate and independent control of the shape and size of both the single-hole and the hollow-core, as well as the functionality of the core surface; this requires precise control of the configurations and interfacial properties of the emulsion templates. However, techniques to achieve this sort of fine control do not exist. Herein, we report a versatile strategy for fabrication of highly controlled hole–shell microparticles with a hollow core and a single, precisely determined hole, and with simultaneous, independent control of the properties of the core interface. W/O/W double emulsions from capillary microfluidics were used as the initial templates for the microparticles. By controlling the composition of the organic middle phase, we varied the adhesion energy DF between the inner drop and outer phase to control the evolution of the emulsions from initial core-shell to the desired acorn-shaped configuration; this produces versatile emulsion templates for controllable fabrication of monodisperse hole-shell microparticles with advanced shapes. Further adjustment of the hole–shell structures can be achieved by changing the size and [*] Dr. W. Wang, M.-J. Zhang, Dr. R. Xie, Dr. X.-J. Ju, C. Yang, C.-L. Mou, Prof. L.-Y. Chu School of Chemical Engineering, Sichuan University Chengdu, Sichuan, 610065 (China) E-mail: [email protected] Homepage: http://teacher.scu.edu.cn/ftp_teacher0/cly/