A Route to Water‐Soluble Molecularly Templated Nanoparticles Using Click Chemistry and Alkyne‐Functionalized Hyperbranched Polyglycerol

Abstract

Cored polymeric nanoparticles were prepared using an adenosine template and allylated hyperbranched polyglycerols (HPGs). The HPGs contained a single alkyne that was capable of 1,3‐dipolar cycloaddition with a decaazido adenosine template to facilitate the rapid synthesis of HPGs containing a large number of allyl end‐groups. Ring closing metathesis (RCM) mediated cross‐linking at high dilution using a Hoveyda‐Grubbs catalyst produced single polymer nanoparticles containing a single template. These particles were rendered water‐soluble through treatment with osmium tetroxide and NMO co‐oxidant. After hydrolytic removal of the template, the nanoparticles were tested for their ability to bind a variety of nucleosides and nucleobases and showed a preference for purine bases over pyrimidine bases. This is the first reported use of hyperbranched polymers for the synthesis of monomolecularly imprinted polymers (mMIPs) as well as the first time monomolecular imprinting has been applied to a homogeneous aqueous system.

Allosteric Control of Photofoldamers for Selecting between Anion Regulation and Double-to-Single Helix Switching

“…Foldamer F1 was synthesized in a straightforward manner using a body–arm approach (Scheme and section S.2). The body was synthesized by installing the azide by the diazonium displacement of the amines on 3,5-diaminobenzoic acid with sodium azide, , followed by amide coupling with a chiral leucine derivative . The arm was synthesized by copper­(I)-catalyzed azide–alkyne cycloaddition (CuAAC) , of 3-azidoazobenzene 2 with trisubstituted phenylene 1 followed by thermal Sonogashira , reaction with trimethylsilylacetylene.…”

Self-Assembling Amphiphilic Hyperbranched Polyglycerol-Polystyrene Copolymers for Encapsulation

“…Indeed, HPGs have been prepared with biomolecular recognition units, H‐bonding units, and host–guest modules or with cross‐linkable moieties that create a more rigid structure. The cross‐linked HPGs have been shown to complex small molecules, including in a photoresponsive fashion, be useful for preparing monomolecularly imprinted polymers (mMIPs), and significantly stabilize fluorophores on their interiors . These applications show how the compact, globular structure of HPGs might facilitate encapsulation and provide a dense, protective layer to reduce leakage.…”