Synthesis of Core Functionalized Polymer Micelles and Shell Cross-Linked Nanoparticles

Abstract

We present the synthesis of novel core reactive spherical polymeric micelles and nanoparticles using nitroxide mediated polymerization (NMP) techniques. These nanostructures have terpyridine functionality selectively located within their hydrophobic core domain and have been further modified by metal complexation (with Fe, Ru, and Cu) within this domain to afford novel metal functionalized polymer nanostructures. The hydrodynamic diameters (D h) of these micelles and hybrid nanoparticles were determined by dynamic light scattering (DLS), and the dimensions of the nanoparticles were characterized using transmission electron microscopy (TEM) and confirmation of the complexation was achieved using UV–vis analysis. The reactivity of the Cu-tethered metal complex within the nanostructures was investigated and was found to be an active catalyst for the 1,3-dipolar cycloaddition “click” reaction of azido and alkynyl functionalized small molecules. This strategy provides a versatile synthetic route toward the selective incorporation of active sites within the core domain of a polymer nanoparticle.

Coordination Chemistry inside Polymeric Nanoreactors: Metal Migration and Cross-Exchange in Amphiphilic Core-Shell Polymer Latexes

“…This resonance corresponds closely in the chemical shift and Rh coupling to that of the related molecular compound [Rh(acac)(CO){P(C 6 H 4 -4-OMe) 3 }] (δ 43.5, J PRh = 175.6 Hz) [45]. It is also essentially identical to that previously reported for [Rh(acac)(CO)(BMOPPP@CCM)] [8] (recalled in the SI, Figure S3).…”

Catalytic polymeric nanoreactors: more than a solid supported catalyst

“…In this case, the core of the particles contained a terpyridine side group that could be utilized as a ligand to bind Cu(I) species. [37] The catalytic efficiency of these nanoparticles on mediating "click'' reactions was confirmed using a fluorogenic reaction between an azido coumarin and an alkynyl small molecule. Further, more recent work by Weck and co-workers used poly(2-oxazoline)-based amphiphilic triBCPs with a salen-functionalized hydrophobic block prepared by living cationic polymerization.…”

“…Hence, a new strategy has been Prospective Article developed which involves the synthesis of functionalized monomers, which can be incorporated selectively into a specific domain of a BCP via robust CRP techniques. [30,[37][38][39][40] This approach allows for the synthesis of functional polymers without the need of protecting groups or post-functionalization steps. [41] The choice of functional monomer provides the possibility of introducing a variety of functional groups into the micelle (core, shell, or surface), which can tune the properties of the nanostructure for different applications.…”

Fluorogenic click reaction

“…The CuAAC reaction was performed between non-fluorescent phenylethynyl and 13 in the presence of the nanoparticle to afford a highly fluorescent solution, which showed the copper complex had been formed and could be used as an active catalyst for the click reaction. 44 In a similar study, the fluorogenic CuAAC reaction with azido-coumarin 13 was used as a general method to functionalize polymer particles, formed by a starve-fed sequential emulsion polymerization process, under gentle conditions. 45 Recently, Cornelissen and coworkers also described the use of the fluorogenic CuAAC to monitor protein-polymer conjugation.…”