Preparation of functional surfaces and protein polymer conjugates via light induced tetrazine click reaction

Abstract

Click reactions have been essential tool for fabrication and modification of functional materials from the beginning of the twenty-first century. After this milestone, several click approach including cycloaddition reactions (Huisgen 1,3‐dipolar cycloaddition, also the Diels-Alder (DA) reactions), nucleophilic ring‐opening reactions, reactions of some carbonyl compounds, thiol‐ene chemistry and Michael additions have been developed. The valuable features including quantitative yields under mild conditions, not producing offensive byproducts and tolerant to many chemical functionalities make this chemistry elegant toolbox in material science and macromolecular engineering. Additionally, some of these reactions are employed in chemical biology and considered as bioorthogonal reactions, since they can occur inside of living systems without interfering with native biochemical processes. Amongst these reactions, Inverse Electron Demand Diels-Alder (IEDDA) Reaction has come into prominence recently, due to its remarkable kinetics and biorthogonality. Polymer chemists endeavor the synthesis of macromolecules, which have advanced architectures (e.g. homopolymers and block copolymers). Combinations of DA "click" reactions with live/controlled polymerization methods are effective solutions to create various architectures, which qualify reversible added fragmentation chain transfer polymerization (RAFT), nitroxide-mediated radical polymerization, atom transfer radical polymerization (ATRP), ring-opening polymerization (ROP). With its high selectivity and super-fast kinetics, the tetrazine-mediated IEDDA Click Reaction is an essential modification technique, which is used in this thesis study. The addition of tetrazine portions to the polymer chains requires a post-polymerization step leading to multi-stage synthetic routes and functional polymeric materials. Such approaches result in the decomposition of the polymer and the molecule, which are specified for modification. In this study, the modification of glass surfaces was made by using the light-induced version of the DA reaction