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. 2025 Apr 29;11(5):331.
doi: 10.3390/gels11050331.

The First Example of a Model Amphiphilic Polymer Conetwork Containing a Hydrophobic Oligopeptide: The Case of End-Linked Tetra[Poly(ethylene glycol)- b-oligo(L-alanine)]

Demetris E Apostolides  1 , George Michael  1 , Costas S Patrickios  1 , Takamasa Sakai  2 , Iro Kyroglou  3 , Maria Kasimatis  3 , Hermis Iatrou  3 , Sylvain Prévost  4 , Michael Gradzielski  5
Affiliations

The First Example of a Model Amphiphilic Polymer Conetwork Containing a Hydrophobic Oligopeptide: The Case of End-Linked Tetra[Poly(ethylene glycol)- b-oligo(L-alanine)]

Demetris E Apostolides et al. Gels. .

Abstract

Herein we describe the development of the first model amphiphilic polymer conetwork (APCN) comprising a short hydrophobic hexa(L-alanine) segment being the outer block of an amphiphilic four-armed star block copolymer with inner poly(ethylene glycol) (PEG) blocks bearing benzaldehyde terminal groups and end-linked with another four-armed star PEG homopolymer (tetraPEG star) bearing aryl-substituted acylhydrazide terminal groups. The present successful synthesis that yielded the peptide-containing model APCN was preceded by several unsuccessful efforts that followed different synthetic strategies. In addition to the synthetic work, we also present the structural characterization of the peptide-bearing APCN in D2O using small-angle neutron scattering (SANS).

Keywords: SANS; amphiphilic polymer conetworks; aqueous swelling; peptides; tetraPEG.

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Conflict of interest statement

The authors declare no conflicy of interest.

Figures

Figure 1
Figure 1
Reaction scheme leading to the four-step transformation of the tetraPEG-OH star into the tetraPEG-b-OAla-Bz star APCN building block.
Figure 2
Figure 2
Size exclusion chromatograms of the tetraPEG-NH2 and tetraPEG-b-OAla-NH2 star polymers.
Figure 3
Figure 3
1H NMR spectra in d6-DMSO of the (a) tetraPEG-b-OAla-NH2 star block copolymer and (b) its end-functionalized derivative tetraPEG-b-OAla-Bz. The peaks labeled DMSO and H2O at 2.5 and 3.5 ppm, respectively, are due to the hydrogenated impurities in the deuterated solvent.
Figure 4
Figure 4
Modification of the tetraPEG-OH star starting polymer to obtain the two main polymeric building blocks, the tetraPEG-b-OAla-Bz end-functionalized amphiphilic star block copolymer and the tetraPEG-Hz end-functionalized hydrophilic star homopolymer, and their end-linking to obtain the desired model APCN.
Figure 5
Figure 5
SANS profile of the peptide-containing APCN in D2O.
See this image and copyright information in PMC

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