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

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.

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2017

Author dc:creator

• Park, Jiwon Victoria

Advisor dc:contributor.advisor

• Jeremiah A. Johnson.

• Chemistry.

Statement dc:rights

• MIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/112447

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/112447