We demonstrate high efficiency and simplicity of the thiol-epoxy reaction towards preparation a wide range main-chain as well end-chain multifunctional polymers.

In this study, we investigate the potential of an artificial structural motif, azobenzene, in preparation enzyme sensitive polymeric nanostructures. For purpose, azobenzene linkage is established at copolymer junction amphiphilic diblock copolymer. This polymer assembles into a micellar structure water. Treatment with azoreductase, presence coenzyme NADPH, results cleavage azo-based and disruption assembly. These suggest that azobenezene useful non-natural motif for responsive nanoparticles....

Know where to fold 'em: A foldamer exhibiting a light-induced helix–coil transition (see scheme) can be constructed by introducing photochromic azobenzene moiety (red) into the center of an amphiphilic phenylene ethynylene backbone (blue). This system gives insight folding and unfolding mechanisms promises applications in photoresponsive (bio)materials “smart” delivery devices based on dynamic receptors.

ABSTRACT Base‐catalyzed reaction between a thiol and an epoxide group is simple fusion process that leads to the formation of β‐hydroxythio‐ether linkage. This efficient, regio‐selective, fast. In addition, it produces reactive hydroxyl upon completion. Therefore, considerable potential in synthesis functional soft materials. Here, we discuss fundamental aspects this process, so‐called thiol‐epoxy “click” reaction, its utility preparation post‐polymerization functionalization polymers...

Single and multiple post-polymerization modifications of poly(glycidyl methacrylate) scaffold through the nucleophilic ring-opening reactions pendent epoxide groups are described.

The thiol–epoxy ‘click’ process is employed as a polymerization reaction to prepare linear polymer chains substituted with free hydroxyl groups. Post-polymerization modification of the units afforded functional polymers exhibiting substituent dependent properties. In this way, functionalized macromolecules are obtained in two simple synthetic steps from commercially available monomer building blocks and reagents.

Catalytic action of an enzyme is shown to transform a non-assembling block copolymer, composed completely non-natural repeat unit structure, into self-assembling polymer building block. To achieve this, poly(styrene) combined with enzyme-sensitive methacrylate-based segment carrying carefully designed azobenzene side chains. Once exposed the azoreductase, in presence coenzyme NADPH, linkages undergo bond scission reaction. This triggers spontaneous 1,6-self-elimination cascade process and...

A simple synthetic strategy has been developed for accessing internally functionalized dendrimers. The key feature of this approach is the use two orthogonal and efficient reactions--'epoxy-amine' 'thiol-ene' coupling--for rapid growth dendritic scaffold. This sequence reactions allows introduction reactive hydroxyl groups at each layer.

By taking advantage of the orthogonal nature thiol−ene coupling and anhydride based esterification reactions, a facile chemoselective strategy to dendritic macromolecules has been developed. The ability interchange growth steps on chemistry allows synthesis fifth-generation dendrimers in only five under benign reaction conditions. In addition, presented chemistries eliminate traditional need for protection/deprotection afford high yield purity. modularity this coupled with latent reactivity...

In this study, we probe various aspects of a post-polymerization double-modification strategy involving sequential thiol–epoxy and esterification reactions for the preparation dual-functional homopolymers.

Dual action: Trackable multifunctional dendritic scaffolds with high internal loading capacity were synthesized based on a PEG core. Orthogonal functionalization of chain-end and groups allowed the dendrimers to be both labeled loaded releasable dyes for simultaneous monitoring carrier release dye payload inside living cells (see picture). Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They...

We report on the strong segregation of core–shell Au nanoparticles, with a shell layer consisting random copolymer brush styrene and vinylphenol (PS-r-PVPh-SH), in poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) diblock copolymer. Because formation multiple hydrogen bonds between hydroxyl groups within nanoparticles pyridine group PS-b-P2VP, were strongly localized into P2VP domains very high volume fraction (ϕp ∼ 0.53). The spatial distribution observed by transmission electron microscopy...

Poly(ß-hydroxyl amine)s are prepared from readily available small molecular building blocks at ambient conditions. These macromolecules can be transformed into main-chain cationic polymers upon quaternization of the backbone amine units. The modular and mild nature synthesis allows for incorporation multiple (2–4) chemically distinct reactive sites in polymer chain. Modifications afford multifunctional with tunable properties. orthogonal involved chemistries sets synthetic pathway free any...

A novel and modular strategy has been developed for the preparation of reactive functionalized hydrogels. In this strategy, thiol–epoxy coupling chemistry was employed formation a hydrophilic network. The hydroxyl groups, generated during process, were then engaged in anchoring fluorescent probe to hydrogel scaffold.

A new synthesis of hyperbranched polymers through proton transfer polymerization thiol and epoxide groups is presented. For this, an AB2 monomer bearing two epoxides a synthesized. Base-catalyzed this led to the formation polythioether-based polymer with 65–69% degree branching carrying about 2% disulfide-based structural defects. This contained reactive sites, hydroxyl group unit, distributed throughout branched scaffold. The could be employed in anchoring alkyl, aryl, or ethylene oxide...

The growing synergy between supramolecular chemistry and polymer synthesis is driven by the realization that dynamic nature of non-covalent interactions may bring new properties material performance to field science. This manifested in area block copolymer self-assembly where systems have displayed remarkable morphologies not attained classic covalent systems. review article examines broad strategy combining phase separation copolymers with interactions.

The tubular secondary structure of a folded helical polymer—a poly(m-phenyleneethynylene) derivative carrying multiple cinnamate moieties—is stabilized by intramolecular cross-linking through topochemically controlled photodimerizations (see schematic representation). This approach should enable the generation organic nanotubes with dimensions and surface functionality that constitute attractive building blocks for functional nanostructures. Supporting information this article is available...

Introduction of photochromic azobenzene units into amphiphilic oligo(meta-phenylene ethynylene)s allowed photocontrol over the helix-coil transition in this important class foldamers. Two design principles were followed efforts to accommodate cis- and trans-azobenzene moieties within helical structure selectively turn state on off, respectively. Several oligomer series with varying connectivities central chromophore synthesized these oligomers investigated regard their folding behavior both...

The synthesis of isomeric, functionalized 4-vinyl-1,2,3-triazole and 5-vinyl-1,2,3-triazole monomers is demonstrated using heterogeneous copper (copper-in-charcoal)-catalyzed azide−alkyne cycloaddition (CuAAC) or homogeneous ruthenium (Ru)-catalyzed cycloadditions (RuAAC) "click" protocols. These reactions are regiospecific, exclusively forming 1,4- 1,5-disubstituted triazoles as determined by 1H NMR, 13C X-ray crystallography analysis. Polymerizations were performed living free radical...

ABSTRACT A synthetic route is developed for the preparation of an AB‐type monomer carrying epoxy and a thiol group. Base‐catalyzed thiol‐epoxy polymerization this gave rise to poly(β‐hydroxythio‐ether)s. systematic variation in reaction conditions suggested that tetrabutyl ammonium fluoride, lithium hydroxide, 1,8‐diazabicycloundecene (DBU) were good catalysts. Triethylamine, contrast, required higher temperatures excess amounts yield polymers. THF water could be used as mediums. However,...

We report polyethylene glycol-based reactive diblock copolymer as well random scaffolds that can be transformed into desired bifunctional copolymers in two synthetic steps. Synthesis of the general is achieved via a controlled atom transfer radical polymerization process while functional groups are introduced thiol–epoxy 'click' and esterification reactions.

A three-step synthetic strategy is established for the preparation of functionalized bottlebrush copolymers. In this scheme, highly efficient nature thiol-epoxy coupling chemistry employed attachment thiol terminated poly(ethylene glycol) (PEG) polymers (0.18, 0.8, and 2 kDa) to poly(glycidyl methacrylate) (PGMA) backbone (25 46 kDa). This reaction resulted in formation water-soluble copolymers (50–426 with grafting densities ranging from 88 97%. The process also produced reactive hydroxyl...

By combining ATRP polymerization with thiol–epoxy 'click' chemistry, a general, efficient, and protection/deprotection-free route is developed for the preparation of chain-end multifunctional polymers.