A Mild and Efficient Approach to Functional Single-Chain Polymeric Nanoparticles via Photoinduced Diels–Alder Ligation
Altintas, O. / Willenbacher, J. / Wuest, K. / Oehlenschlaeger, K. / Krolla-Sidenstein, P. / Gliemann, H. / Barner-Kowollik, C. (2013)
Macromolecules 46 (2013), 20, 8092-8101
- Date: 2013
Altintas, O. / Willenbacher, J. / Wuest, K. / Oehlenschlaeger, K. / Krolla-Sidenstein, P. / Gliemann, H. / Barner-Kowollik, C. (2013): „A Mild and Efficient Approach to Functional Single-Chain Polymeric Nanoparticles via Photoinduced Diels–Alder Ligation“. In: Macromolecules 46 (2013), 20, 8092-8101
We present a new ambient temperature synthetic approach for the preparation of single-chain polymeric nanoparticles (SCNPs) under mild conditions using a UV-light-triggered Diels–Alder (DA) reaction for the intramolecular cross-linking of single polymer chains. Well-defined random copolymers with varying contents of styrene (S) and 4-chloromethylstyrene (CMS) were synthesized employing a nitroxide-mediated radical polymerization (NMP) initiator functionalized with a terminal alkyne moiety. Postpolymerization modification with 4-hydroxy-2,5-dimethylbenzophenone (DMBP) and an N-maleimide (Mal) derivative led to the functional linear precursor copolymers.
The intramolecular cross-linking was performed by activating the DMBP groups via irradiation with UV light of 320 nm for 30 min in diluted solution (cPolymer = 0.017 mg mL–1). The ensuing DA reaction between the activated DMBP and the Mal groups resulted in well-defined single-chain polymeric nanoparticles. To control the size of the SCNPs, random copolymers with varying CMS contents (i.e., different functional group densities (FGD)) were employed for the single-chain collapse.
Additionally, monotethered nanoparticles were prepared via the copper-catalyzed azide–alkyne cycloaddition between the alkyne bearing copolymer with the highest FGD and an azide-terminated poly(ethylene glycol) (PEG) prior to UV-induced cross-linking. The formation of SCNPs was followed by size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) spectroscopy, dynamic light scattering (DLS), and atomic force microscopy (AFM).