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Asymmetric branched macromolecules, commonly referred to as miktoarm polymers, possess unique topological structures and physico-chemical properties, which make them promising candidates for applications in therapeutics and theranostics. The multiple polymeric arms of varied compositions in miktoarm stars present a platform with immense potential to tailor loading capacities of active pharmaceutical agents, and introduce multitasking units at the outer periphery or in the interior of self-assembled nanostructures. One of the key challenges in the past in the development of nanocarriers based on miktoarm polymers was their fabrication with a precise number of different polymeric segments, which required complex synthetic procedures and stringent purification protocols. With the advances in synthetic methodologies, a variety of miktoarm stars have been developed with demonstrated enhanced nanocarrier stability, high drug loading capability, controlled release profile, and stimulus responsiveness. This chapter describes the advances in the synthesis of miktoarm polymers, and the advantages of synthetically articulated precise branched structures in the design of intelligent nanoscale systems for biological applications, especially in drug delivery and multitasking.

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