Thesis advisor: Jeffery A. Byers / Thesis advisor: Petter Zhang / This thesis discusses the development of a surface-initiated N-carboxyanhydride (NCA) polymerization system from a redox-switchable catalyst for polyamide synthesis and further efforts towards the synthesis of polypeptide-based materials through the integration of NCA synthesis and its polymerization. In Chapter one, the most used methods to obtain polypeptide-based materials as well as their significant limitations are introduced. A new strategy is presented to access the polypeptide-based materials based on the integrated catalysis under spatial and temporal control. In Chapter two, a strategy to allow the attachment of a redox-switchable NCA polymerization catalyst on surface of titania for the synthesis of polyamide brushes will be demonstrated. Investigations about the kinetics of this surface-initiated ring-opening polymerization will be presented by carrying out the reaction in batch and under flow. Chapter three will discuss efforts towards achieving the integration of NCA synthesis and NCA polymerization, which includes an additional anchoring method to support polymerization catalyst and compatibility tests between the two separate reactions. / Thesis (MS) — Boston College, 2022. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: Jeffery A. Byers / This dissertation discusses the development of catalytic systems within the context of polymer synthesis and functionalization towards the fulfillment of circular plastic economy. Chapter 1 provides an overview of the limitations of the current mechanical recycling for plastic disposal and two general ways to improve the current system by chemical strategies. Chapter 2 discusses the development of a chemically recyclable thermoplastic elastomer derived from relatively cheap feedstock using redox-switchable polymerization. Chapter 3 describes the application of C-H activation and cross-coupling strategy on commodity polyolefins and the effect on the polymer physiochemical properties by the introduction of functional groups, which has the potential to serve in polymer upcycling. Chapter 4 describes the dehydrogenation of polyethylene (PE) and polypropylene (PP) along with further functionalization of the unsaturated product to demonstrate a route of synthesizing PE/PP compatibilizers from plastic waste. Chapter 5 summarizes our development of simulation-based methods to obtain kinetic information of transition-metal catalyzed copolymerization that may include reversible propagation. / Thesis (PhD) — Boston College, 2024. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.