Self-organized polyelectrolyte end-grafted layers under nanoconfinement

Mario Tagliazucchi, Xing Li, Monica Olvera De La Cruz, Igal Szleifer*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

15 Scopus citations


Layers of end-grafted weak polyelectrolytes in poor solvent self-organize into a rich variety of structures (such as micelles, micelles coexisting with nonaggregated chains, stripes and layers with solvent-filled holes) due to the subtle competition among hydrophobic, electrostatic and steric interactions and the chemical acid-based equilibria of the weak polyelectrolyte. In this work, a molecular theory has been used to systematically study how nanoconfinement modulates the competition among these interactions and, therefore, dictates the morphology of the self-assembled layer. Two different types of confinement were considered and compared: (i) soft lateral confinement due to increasing surface coverage in a planar polyelectrolyte brush and (ii) hard vertical confinement due to the interaction of a planar polyelectrolyte brush with an opposing surface, as typically found in AFM-colloidal-tip and surface-force-apparatus experiments. It is shown that increasing the surface coverage (soft lateral confinement) or compressing the layer with an opposing wall (hard vertical confinement) have a similar qualitative effect on the morphology of the system: both types of nanoconfinement increase the stability of morphologies that extend in one or two dimensions (such as the homogeneous brush, holes and stripes) over nonextended aggregates (such as hemispherical micelles). However, vertical confinement can also lead to pillar-like structures that are not observed in the absence of the opposing wall. Interestingly, the pillar structures, which bridge the grafting and opposing surfaces, may coexist with metastable structures collapsed to the grafting surface only. This coexistence may help to understand the hysteresis commonly observed in surface-force experiments.

Original languageEnglish (US)
Pages (from-to)9998-10008
Number of pages11
JournalACS nano
Issue number10
StatePublished - Oct 28 2014


  • aggregates
  • molecular interactions
  • pH
  • polyelectrolyte brush
  • poor solvent

ASJC Scopus subject areas

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)


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