Bioinspired Polymeric High Aspect Ratio Particles with Asymmetric Janus Functionalities.

Polymeric particles with intricate morphologies and properties have been developed based on bioinspired designs for applications in regenerative medicine, tissue engineering, and drug delivery. However, the fabrication of particles with asymmetric functionalities remains a challenge. Janus polymeric particles are an emerging class of material with asymmetric functionalities; however, they are predominantly spherical in morphology, made from non-biocompatible materials, and made using specialized fabrication techniques. We therefore set out to fabricate nonspherical Janus particles inspired by high aspect ratio filamentous bacteriophage using polycaprolactone polymers and standard methods. Janus high aspect ratio particles (J-HARPs) were fabricated with a nanotemplating technique to create branching morphologies selectively at one edge of the particle. J-HARPs were fabricated with maleimide handles and modified with biomolecules such as proteins and biotin. Regioselective modification was observed at the tips of J-HARPs, likely owing to the increased surface area of the branching regions. Biotinylated J-HARPs demonstrated cancer cell biotin receptor targeting, as well as directional crosslinking with spherical particles via biotin-streptavidin interactions. Lastly, maleimide J-HARPs were functionalized during templating to contain amines exclusively at the branching regions and were dual-labeled orthogonally, demonstrating spatially separated bioconjugation. Thus, J-HARPs represent a new class of bioinspired Janus material with excellent regional control over biofunctionalization.