Design of PolyMOCs and the synthesis of crosslinkers for the BASP platform

Abstract

In Chapter 1, two stepwise assembly strategies for the integration of metal-organic cages (MOCs) into polymers were explored. The first strategy creates Block Co-PolyMOCs (BCPMOCs), which feature the integration of MOCs into block copolymers (BCPs). In the first assembly step, BCPs functionalized with a bispyridyl ligand on the chain end undergo Pd induced MOC assembly. In the second step, microphase separation of BCPs is induced, introducing a physical cross-link between the star polymers and producing the desired BCPMOC networks in the bulk or gel state. In the second strategy, another orthogonal interaction is explored to create a different type of polyMOC. In this case, poly(methyl acrylate) (PMA) homopolymers are synthesized from initiators featuring a diene or dienophile on one end and functionalized with a bispyridyl ligand on the other end. Diels-Alder (DA) cycloaddition is used in the second step to create a polyMOC network. Given the functional diversity of MOCs, both strategies should enable access to materials with a wide range of properties and applications. Chapter 2 outlines the synthesis of norbornene macromonomers (MMs) with varying anchor groups and crosslinkers that are stimuli-sensitive for the brush-arm star polymer (BASP) drug delivery platform. Variation of MM anchor groups modifies the rate of propagation of ring-opening metastasis polymerization (ROMP), while the design of crosslinkers that are acid- and photo-labile contributes to the expansion of a wide-ranging library of crosslinkers for drug loading and release. The brush-first ROMP polymerization strategy allows for the synthesis of BASPs for single drug or multiple drug combinations.