Recent progress with multicompartmental nanoparticles

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Introduction Nano- and microparticles have demonstrated exceptional potential in a variety of areas, such as diagnostics, therapeutics, and energy applications.1 Recent improvements in particle fabrication methods, such as the expansion of compositional flexibility and physical as well as chemical tunability, have resulted in increased functional versatility of colloidal particles. In particular, precise engineering of shape, size, surface structures, and mechanical properties has been accomplished by several processes.2–4 Beyond the current state of the art, the complementary control of internal (bulk) and external (surface) features has emerged as an important design parameter for multifunctional particles, where the bulk and surface of each particle are no longer isotropic in their functionality and characteristics. These anisotropic particles may feature two or more distinct compartments, controlled interfacial patterns, or compositionally distinct material domains in a single particulate entity.5–15 Novel self-assembled particles, such as multifunctional particles, may find diverse applications in multiplexed bioassays,16 vehicles for multiple therapeutic modalities,17 biohybrid materials,18 or microactuators.19,20 Compositional bulk anisotropy may enable unique particle properties. Here, a particle configuration that features materials compartmentalized within a monolithic particle can impart entirely new properties and may be a decisive functional parameter, being similarly as important as the actual chemical

makeup.4 On the other hand, anisotropic surface functionalization can be realized in the form of patchy particles, where different surface patches are associated with different chemically or functionally orthogonal surface properties. Particles with this type of surface anisotropy can exhibit bipolar characteristics, such as particles that are simultaneously hydrophilic and hydrophobic, or can be used for self-assembly and drug delivery.21–23 Independent control of the compositions of individual compartments of the same particle allows for inclusion of materials with highly dissimilar sets of properties. This approach forms the foundation for the controlled release of multiple drugs with independent release kinetics (provided that each drug is loaded in a separate compartment) or a combination of fully decoupled modalities for combined imaging and therapy (theranostics) (see the article by Yhee et al. in this issue).24 In addition, selective surface functionalization of individual compartments remains a possibility and may lead to even more versatile and multifunctional particles. Compartmentalized particles can be fabricated by a range of different methods. In particular, the self-assembly of block copolymers25,26 or the use of intended phase separation during seeded polymerizations (where two non-miscible solvents are used to create an emulsion, at the interface of which two different polymer brushes are grown on the same nucleation seed), are widely pursued approaches toward anisotropic nanoparticles.2