Nanostructured Surfaces through Immobilization of Self‐Assembled Polymer Architectures Using Thiol–Ene Chemistry

Abstract

An efficient strategy for engineering nanostructured surfaces by coupling soft polymeric nanoarchitectures to functionalized surfaces is presented. Self‐assembly of polymeric nanoarchitectures from amphiphilic triblock copolymers can yield both filled and hollow spherical nanoarchitectures, depending on the properties of the polymer chosen. These nanoarchitectures are immobilized on solid substrates via a biocompatible thiol–ene reaction, and conditions are optimized to maintain structural integrity of polymeric assemblies. Two routes of surface modification are also implemented to allow inclusion of a polymeric spacer that can mediate between soft polymeric assemblies and solid substrates. Nanostructured surfaces with both filled and hollow nanoarchitectures attached to the surface directly or with a spacer are successfully generated with this protocol. This concept of generating nanostructured surfaces using preassembled polymeric architectures is an important step toward active surfaces, because entrapment of active molecules in the nanoarchitectures prior to their immobilization opens the door to easy generation of surfaces with predetermined activities.

Surfaces Decorated with Polymeric Nanocompartments for pH Reporting

“…Since our method is geared towards translational application, we have opted to immobilize our vesicles on glass, rather than much more expensive silicon wafers. As an attachment strategy, we used a thiol‐ene click chemistry procedure . Glass surfaces were solvent‐cleaned and activated in a plasma chamber, which generates reactive ‐OH groups on the surface.…”

“…Next, the activated glass plates were functionalized using a 3‐(mercaptopropyl)trimethoxysilane linker. It was previously shown that the terminal thiol group of the selected linker reacts efficiently with the terminal methacrylate groups of the polymer . The reaction between the thiol groups on the glass substrate, and the methacrylate groups of polymer chains was performed in the presence of pH‐adjusted TCEP (tris(2‐carboxyethyl) phosphine hydrochloride) catalyst, thereby anchoring the nanocompartments to the glass surface.…”

“…Glass cover slips (approximate size 0.7 cm × 2 cm) were functionalized with a 3‐(mercaptopropyl)trimethoxysilane linker according to previously published procedures . Clean glass cover slips were O 2 plasma treated for 10 min, submerged in a solution of 10 mL anhydrous toluene, 13 μL trimethylamine and 3 μL silane linker and allowed to react at room temperature under constant shaking.…”

Self‐Assembled Polymeric Membranes and Nanoassemblies on Surfaces: Preparation, Characterization, and Current Applications

“…The surface modification spans from chemical functionalization with small molecules that serve as initiators or reactive braces for self‐assembled monolayers (SAM). Common functionalization is based on highly reactive molecules that undergo high yielding chemistry, such as EDC/NHS, “Click,” thiol–ene, and Sn2 chemistry . Since the polymer chains are produced in advance, high control over the brush thickness is achieved by controlling the chain length.…”

“…The immobilization of nanostructures is performed either via non‐specific binding, or by covalent or supramolecular bonding . Among the three, the latter is preferred as it allows achieving higher control over the binding topology and distribution, as it has been reported by exploiting strain promoted click chemistry and thiol–ene reactions . The metal‐free highly reactive moieties (cyclooctine with azide) allowed the facile decoration of the PMOXA‐PDMS‐PMOXA assemblies on the surface.…”