The molecular shape of poly(propylenimine) dendrimer amphiphiles has a profound effect on their self assembly

Kar Wai Chooi, Alexander I Gray, Laurence Tetley, Yuling Fan, Ijeoma F Uchegbu

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

The shape of dendrimer amphiphiles has an unexpected effect on their self-assembly. A series of diaminobutane poly(propylenimine) generation 3 dendrimer (DAB-dendr-(NH(2))(16)) amphiphiles has been synthesized, bearing an average of five (PD5), three (PD3) and one (PD1) palmitoyl group(s) per dendrimer molecule. Additionally DAB-dendr-(NH(2))(16) was derivatized with a layer of poly(ethylene glycol) (PEG, degree of polymerization = 12) groups and conjugated to an average of 1 palmitoyl group at the PEG end (PPD1). A final amphiphile resulted from the conjugation of DAB-dendr-(NH(2))(16) with 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-succinimidylpropionate (DSPE-PEG(3400)-SPA), i.e.: DPD5 (with 4 DSPE-PEG arms). The critical micellar concentration in aqueous media followed the trend: DPD5 <PD5 = PD3 <PD1 <PPD1 and amphiphiles eventually formed 10-20 nm monomolecular or multimolecular micelles and/or 200 nm spheres or tubules. Aggregation was entropy driven, as expected, for DPD5, PD5 and PD1 and enthalpy driven with the most hydrophilic compound PPD1, but was unexpectedly enthalpy driven for PD3. PD3 aggregates formed low capacity hydrophobic domains with a limited capacity for encapsulation of cyclosporine A; encapsulation levels (mole drug per mole polymer) were 0.099, 0.014, 0.099, and 0.735 for PD1, PD3, PD5, and DPD5 and, respectively. We conclude that star shaped amphiphiles such as PD3 are sterically hindered from self-assembling into high capacity hydrophobic domains in aqueous media. Amphiphile-membrane interactions were promoted by hydrophobic groups, but diminished by PEG moieties. DPD5 is the most suitable amphiphile for biomedical applications.
Original languageEnglish
Pages (from-to)2301-2316
Number of pages16
JournalLangmuir
Volume26
Issue number4
Early online date27 Oct 2009
DOIs
Publication statusPublished - 2009

Keywords

  • dendrimers
  • micelles
  • molecular structure
  • particle size
  • polypropylenes
  • surface properties
  • surface-active agents
  • thermodynamics

Fingerprint Dive into the research topics of 'The molecular shape of poly(propylenimine) dendrimer amphiphiles has a profound effect on their self assembly'. Together they form a unique fingerprint.

Cite this