Multifunctional Surface Manipulation Using Orthogonal Click Chemistry

Abstract

Polymer brushes are excellent substrates for the covalent immobilization of a wide variety of molecules due to their unique physicochemical properties and high functional group density. By using reactive microcapillary printing, poly(pentafluorophenyl acrylate) brushes with rapid kinetic rates toward aminolysis can be partially patterned with other click functionalities such as strained cyclooctyne derivatives and sulfonyl fluorides. This trireactive surface can then react locally and selectively in a one pot reaction via three orthogonal chemistries at room temperature: activated ester aminolysis, strain promoted azide-alkyne cycloaddition, and sulfur(VI) fluoride exchange, all of which are tolerant of ambient moisture and oxygen. Furthermore, we demonstrate that these reactions can also be used to create areas of morphologically distinct surface features on the nanoscale, by inducing buckling instabilities in the films and the grafting of nanoparticles. This approach is modular, and allows for the development of highly complex surface motifs patterned with different chemistry and morphology.

Combining Click Sulfur(VI)‐Fluoride Exchange with Photoiniferters: A Facile, Fast, and Efficient Strategy for Postpolymerization Modification

“…SuFEx was used to “click” a silyl ether rapidly and quantitatively to a polymer containing native SO 2 F groups . Since dye‐modified polymers have been widely used in a range of biological applications including fluorescent sensors, probes, and agents for cell imaging, Disperse Red 1 was selected as a model small molecule dye for attachment at the polymer chain‐ends and quantification of the SuFEx click reaction.…”

“…The SuFEx reaction has become recognized as a superior approach for postpolymerization modification in polymer synthesis, surface functionalization, and other forms of polymer materials engineering. For example, the SuFEx reaction was recently used by Locklin and co‐workers for the postmodification of polymer brushes on surfaces . These studies demonstrated that SuFEx can be used to introduce other types of click functionalities into polymer scaffolds.…”

“Shine & Click” Photo‐Induced Interfacial Unmasking of Strained Alkynes on Small Water‐Soluble Gold Nanoparticles

“…The Popik group reported a cyclopropenone‐masked dibenzocyclooctyne (DIBO) that undergoes clean decarbonylation under ultraviolet A (UV‐A) irradiation to afford DIBO . They have also demonstrated the application of these cyclooctyne precursors in the surface functionalization of patterned polymer brush films . However, derivatization of AuNPs or Au surfaces with cyclopropenone‐masked DIBO moieties has never been reported.…”

“…[37] They have also demonstrated the applicationo ft hese cyclooctyne precursors in the surfacef unctionalization of patterned polymer brush films. [38][39][40][41] However, derivatization of AuNPs or Au surfaces with cyclopropenone-masked DIBO moieties has never been reported. Such masked cyclooctynes are unreactivet owards azides or nucleophiles in the absence of UV light, thus making it the ideal precursor for incorporation onto AuNPs to overcome the limitations previously described.…”

Preparation of Functional Alternating Polymer Brushes and Their Orthogonal Surface Modification through Microcontact Printing

“…μCP was also used to conjugate amines through aminolysis on polyester brushes. As the amines carried an additional and orthogonal reactive group, the polymer surface could be modified in a second post‐modification step . In another study, μCP on polymer brushes was used to control the surface patterning at defined distances by variation of the printing pressure …”