Probing secondary coordination sphere interactions within porphyrin-cored polymer nanoparticles

A suite of zinc porphyrin-cored random coil polymers and polymeric nanoparticles with varying degrees of potential hydrogen bonding character and steric bulk were synthesized and characterized to study secondary coordination sphere interactions. The reaction of cyanide with N,N-dimethylformamide in the presence of porphyrin-cored polymeric nanoparticles was monitored via UV-Vis spectroscopy. It is shown that the zinc porphyrin-cored polymers and nanoparticles catalyzed the reaction of cyanide with N,N-dimethylformamide with the highest reaction rates occurring with polymeric nanoparticles with a greater number of potential hydrogen bond donors and greater steric bulk

100th Anniversary of Macromolecular Science Viewpoint: Re-examining Single-Chain Nanoparticles

Single-chain nanoparticles (SCNP) are a class of polymeric nanoparticles obtained from the intramolecular cross-linking of polymers bearing reactive pendant groups. The development of SCNP has drawn tremendous attention since the fabrication of SCNP mimics the self-folding behavior in natural biomacromolecules and is highly desirable for a variety of applications ranging from catalysis, nanomedicine, nanoreactors, and sensors. The versatility of novel chemistries available for SCNP synthesis has greatly expanded over the past decade. Significant progress was also made in the understanding of a structure–property relationship in the single-chain folding process. In this Viewpoint, we discuss the effect of precursor polymer topology on single polymer folding. We summarize the progress in SCNP of complex architectures and highlight unresolved issues in the field, such as scalability and topological purity of SCNP

Tuning the size of supramolecular single-chain polymer nanoparticles

In this article we further investigate our recently devised method for folding polymer chains into nanoparticles using intramolecular, supramolecular interactions. Specifically, we show a direct relationship between molecular weight of the parent chain and size of the folded nanoparticle. This is investigated both analytically via the separation and subsequent characterization of a polydisperse nanoparticle sample into high and low molecular weight fractions, and by examining a family of poly(norbornenes) deliberately prepared with varying molecular weights. With these polymer nanoparticles in hand their assembly on surfaces is studied where larger structures are formed as a result of the interplay between the movement of the nanoparticles on the surface and the evaporation of solvent

Single-chain polymernanoparticlesvia reversible disulfide bridges

We report the fabrication of single-chain polymer nanoparticles (SCNP) that can reversibly undergo a coil to particle transition via formation and cleavage of intramolecular disulfide cross-links. Characterization of this behaviour via shifts in SEC retention time confirm the changes in solution conformation in response to oxidative or reductive stimuli.</p