Poly(norbornene)-based random copolymers possessing either azide, aldehyde, or ketone functionalities on each repeating unit were synthesized using ring-opening metathesis polymerization. The orthogonal functionalization of the resulting copolymers using 1,3-dipolar cycloadditions and hydrazone formations was investigated. While the azide- and aldehyde-containing copolymers were insoluble in organic solvents, the azide- and ketone-functionalized copolymers were fully soluble in common solvents such as CH2Cl2, THF, and DMF and can be quantitatively functionalized with a library of small organic and biological molecules in a stepwise fashion. The orthogonal functionalization of the ketone/azide copolymers was characterized by NMR and IR spectroscopies and gel-permeation chromatography. A one-pot dual functionalization strategy is also presented that allows for the quantitative dual functionalization of copolymers. This one-pot strategy introduced herein for the preparation of multifunctional macromolecules provides a modular platform for potential applications ranging from electronic materials to polymer-mediated drug delivery.

Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers. Such materials combine the microphase separation behavior inherent to block copolymers with the responsiveness of supramolecular materials thereby affording dynamic and reversible materials. This tutorial review covers recent advances in main-chain supramolecular block copolymers and describes the design principles, synthetic approaches, advantages, and potential applications.

Colloids with high-symmetry patches are functionalized with metal-coordination-based recognition units and assembled into larger chain architectures, demonstrating for the first time the use of metal coordination as a specific force in colloidal self-assembly. The cross-linked poly(styrene)-based patchy particles are fabricated by encapsulation of colloidal clusters following a two-stage swelling and polymerization methodology. The particle patches, containing carboxylic acid groups, are site-specifically functionalized either with a triblock copolymer (TBC), bearing primary alcohols, alkyl chains, and palladated pincer receptors, synthesized by ring-opening metathesis polymerization, or with a small molecule bearing a pyridine headgroup. Functionalizing with a TBC provides design flexibility for independently setting the range of the interaction and the recognition motif.