Predicting Monomers for Use in Polymerization‐Induced Self‐Assembly

Abstract

We report an in silico method to predict monomers suitable for use in polymerization-induced self-assembly (PISA). By calculating the dependence of LogP oct /surface area (SA) on the length of the growing polymer chain, the change in hydrophobicity during polymerization was determined. This allowed for evaluation of the capability of am onomer to polymerize to form self-assembled structures during chain extension. Using this method, we identified five new monomers for use in aqueous PISA via reversible addition-fragmentation chain transfer (RAFT) polymerization, and confirmed that these all successfully underwent PISA to produce nanostructures of various morphologies.The results obtained using this method correlated well with and predicted the differences in morphology obtained from the PISA of blockc opolymers of similar molecular weight but different chemicalstructures.Thus,wepropose this method can be utilized for the discovery of new monomers for PISA and also the prediction of their self-assembly behavior.

Unique aqueous self-assembly behavior of a thermoresponsive diblock copolymer

“…Recent in silico studies and preliminary experimental data suggest that HBA should be a suitable core-forming block for aqueous PISA. 54 Indeed, the 20% w/w dispersion of PDMAC 56 -P(HBA-stat-DAAM) 264 diblock copolymer nano-objects prepared herein formed a free-standing gel at 25 C (Fig. 2).…”

PISA: construction of self-organized and self-assembled functional vesicular structures

“…O'Reilly and coworkers demonstrated a method to predict the compatibility of coreforming blocks for aqueous PISA, based upon the log P value per unit surface area of the core-forming block. 54 This included the correlation between differences in the obtained morphologies and hydrophobicity of the core-forming block.…”

RAFT‐vermittelte polymerisationsinduzierte Selbstorganisation (PISA)

“…Wie bereits erwähnt, haben Mathers, O'Reilly und Mitarbeiter einen Zusammenhang zwischen der chemischen Natur der zu polymerisierenden Monomere und der Morphologie der erhaltenen Partikel gezeigt, indem sie die wässrige Dispersionspolymerisation von zunehmend hydrophoben Monomeren mittels einer In‐silico‐Methode verglichen. Unter ansonsten identischen experimentellen Bedingungen wechselten die Morphologien mit zunehmender Hydrophobie der Monomere von sphärischen Partikeln zu Würmern und Vesikeln . An und Mitarbeiter synthetisierten eine Reihe von Alkyl‐α‐Hydroxymethylacrylaten mit einstellbarer Wasserlöslichkeit, um die Auswirkungen der Monomerlöslichkeit auf die entstehende Morphologie systematisch zu untersuchen .…”