Light‐driven atom transfer radical polymerization on supramolecular complexes of conjugated polymers and single‐walled carbon nanotubes

Abstract

Previous approaches used to decorate latently reactive conjugated polymer-coated carbon nanotube complexes have utilized "grafting-to" strategies. Here, we coat the carbon nanotube surface with a conjugated polymer whose side chains contain the radical initiator, α-bromoisobutyrate, which enables atom transfer radical polymerization (ATRP) from the polymernanotube surface. Using light to generate Cu(I) in situ, ATRP is used to grow narrow dispersity polymer chains from the polymer-nanotube surface. We confirm the successful polymerization of (meth)acrylates from the polymer-nanotube surface using a combination of gel permeation chromatography and infrared spectroscopy. Strikingly, we demonstrate that nanotube optoelectronic properties are preserved after radical-mediated polymer grafting using Raman spectroscopy and photoluminescence mapping. Overall, this work elucidates a method to grow narrow dispersity polymer chains from the polymernanotube surface using light-driven radical chemistry, with concurrent preservation of nanotube optoelectronic properties.We first explored conditions for light-driven ATRP using methyl methacrylate (MMA). While there are several options available to generate Cu(I) in situ to improve oxygen tolerance Additional supporting information may be found in the online version of this article.

Room‐Temperature Hydrogen Sensor with High Sensitivity and Selectivity using Chemically Immobilized Monolayer Single‐Walled Carbon Nanotubes

“…[ 29 ] Azide‐functionalized polyfluorene was synthesized for the conjugated polymer wrapping method to separate sc‐SWNTs. [ 29,30 ] The absorption and Raman scattering spectra showed the purity of the sc‐SWNTs to be higher than 99%, which is ideal for gas‐sensor applications. The sc‐SWNTs were anchored to an alkyne adhesive polymer‐layer‐coated SiO 2 /Si substrate for chemical immobilized through a Cu‐catalyzed azide–alkyne cycloaddition reaction (see the Experimental section for further information).…”

99mTc-Functionalized Single-Walled Carbon Nanotubes for Bone Targeting

“…By coating the SWNT surface with a CP containing functional groups (FGs) in its side chains, facile reactions can be used to alter the dispersability, , hydrophilicity, stimulus-responsiveness, , and surface adhesion of the polymer–SWNT complex. This strategy can also be extended to polymer grafting from the polymer–SWNT surface via radical polymerization, while preserving SWNT sidewall integrity . SWNTs possess a high aspect ratio and surface area that enable them to efficiently penetrate biological membranes and accumulate into intracellular compartments .…”

“…This strategy can also be extended to polymer grafting from the polymer−SWNT surface via radical polymerization, while preserving SWNT sidewall integrity. 10 SWNTs possess a high aspect ratio and surface area that enable them to efficiently penetrate biological membranes and accumulate into intracellular compartments. 11 In 2006, carbon nanotubes (CNTs) were shown to promote the proliferation of osteocytes and osteoblasts, 12 leading to several in vitro studies demonstrating that CNTs could promote repair in bone-related cells without inflammation or rejection.…”