Functional Polymeric Microparticles Engineered from Controllable Microfluidic Emulsions

Functional polymeric microparticles with typical sizes of 1-1000 μm have received considerable attention for many applications. Especially in biomedical fields, polymeric microparticles with advanced functions such as targeted delivery, controlled encapsulation, or "capture and release" show great importance as delivery systems for active molecules and drugs, as imaging agents for analytics and diagnostics, as microreactors for confined bioreactions, and more. Generally, the functions of these microparticles rely on both their structures and the properties of their component materials. Thus, creating unique structures from functional materials provides an important strategy for developing advanced functional polymeric microparticles. Several methods, such as dispersion polymerization, precipitation polymerization, copolymer self-assembly, and phase-separated polymer precipitation can be used to make functional microparticles, but each has limitations, for example, their limited control over the particle size and structure. Using emulsions as templates, however, allows precise control over the size, shape, composition, and structure of the resulting microparticles by tuning those of the emulsions via specific emulsification techniques. Microfluidic methods offer excellent control of emulsion droplets, thereby providing a powerful platform for continuous, reproducible, scalable production of polymeric microparticles with unprecedented control over their monodispersity, structures, and compositions. This approach provides broad opportunities for producing polymeric microparticles with novel structure-property combinations and elaborately designed functions. In this Account, we highlight recent efforts in microfluidic fabrication of advanced polymeric microparticles with well-designed functions for potential biomedical applications, and we describe the development of microfluidic techniques for producing monodisperse and versatile emulsion templates. We begin by describing microparticles made from single emulsions and then describe those from complex multiple emulsions, showing how the resulting microparticles combine novel structures and material properties to achieve their advanced functions. Monodisperse emulsions enable production of highly uniform microparticles of desired sizes to achieve programmed release rates and passive targeting for drug delivery and diagnostic imaging. Phase-separated multiple emulsions allow combination of a variety of functional materials to generate compartmental microparticles including hollow, core-shell, multicore-shell, and hole-shell structures for controlled encapsulation and release, selective capture, and confined bioreaction. We envision that the versatility of microfluidics for microparticle synthesis could open new frontiers and provide promising and exciting opportunities for fabricating new functional microparticles with broad implications for myriad fields.