Enzyme‐Responsive Polymer Nanoparticles via Ring‐Opening Metathesis Polymerization‐Induced Self‐Assembly

Abstract

Open-to-air aqueous-phase ring-opening metathesis polymerization-induced self-assembly (ROMPISA) is reported for forming well-defined peptide polymer nanoparticles at room temperature and with high solids concentrations (10 w/w%). For these materials, ROMPISA is shown to provide control over molecular weight with high conversion while open-to-air. Moreover, these peptide polymer nanoparticles can spontaneously rearrange into larger aggregate scaffolds in the presence of the proteolytic enzyme, thermolysin. This work demonstrates the robust nature of ROMPISA, highlighted here for the preparation of stimuli-responsive nanostructures in one pot, in air.

Ultraschnelle Synthese multivalenter radikalischer Nanopartikel durch ringöffnende Metathesepolymerisations‐induzierte Selbstorganisation

“…RDRP wird jedoch häufig bei erhöhten Temperaturen durchgeführt und kann beim Abkühlen (manchmal vorteilhaft) morphologische Umwandlungen bewirken . ROMP ist in dispergierten Medien bei moderaten Temperaturen möglich und ist eine vielversprechende alternative Route für die Durchführung von PISA, wie in Arbeiten gezeigt wurde, die im Verlauf dieser Studie veröffentlicht wurden . Am wichtigsten ist, dass ROMP‐Katalysatoren eine hohe Reaktivität und zugleich eine ausgezeichnete Toleranz gegenüber funktionellen Gruppen aufweisen, besondere bei Verbindungstypen, die von RDRP nicht (gut) toleriert werden, wie Alkine, Spezies mit hohem Schwefelgehalt, Thiole und stabile Radikale .…”

Ring-opening metathesis polymerization-induced self-assembly (ROMPISA)

“…55 Building on this concept, the same group prepared enzyme-responsive spherical micelles and phaseseparated framboidal vesicles, following a similar one-pot aqueous-phase ROMPISA methodology. 56 In particular, a hydrophilic PNB block bearing a 15-peptide sequence was first synthesized using the same water-soluble HG2 catalyst by open-to-air ROMP in water at ambient temperature. Nano-object formation was achieved via aqueous dispersion ROMPISA using PMX as the core-forming block, whilst enzymatic cleavage of the corona peptide pendant groups by the proteolytic enzyme thermolysin resulted in occurrence of morphological transitions toward larger aggregates induced by changes in the packing parameter of the assemblies, highlighting their potential use in biomedical applications.…”

Polymerization‐Induced Self‐Assembly

“…Three articles propose the synthesis of stimuli-responsive particles. While Gianneschi et al inserted peptide sequences in the particle shell that could be cleaved via enzymes inducing particle degradation/aggregation, [10] the teams of Boyer [18] and Lacombe and Save [13] designed photo-active particles. Boyer et al propose the insertion of 1-pyrenemethyl methacrylate as a comonomer in the solvophobic block, as a means to photochemically trigger particle dissociation by cleavage of pyrene moieties leading to a solvophobic-solvophilic transition of the core polymer.…”

“…While Gianneschi et al. inserted peptide sequences in the particle shell that could be cleaved via enzymes inducing particle degradation/aggregation, the teams of Boyer and Lacombe and Save designed photo‐active particles. Boyer et al.…”

“…Whereas the great majority of the particles were synthesized via RDRP techniques, implementation of ROMP for PISA in water is also reported, either in dispersion or in emulsion . Stable diblock copolymer particle dispersions could be successfully synthesized using both polymerization processes, but the formation of anisotropic morphologies or vesicles was not observed.…”