Multiple Topologies from Glycopolypeptide–Dendron Conjugate Self-Assembly: Nanorods, Micelles, and Organogels

Abstract

Glycopolypeptides (GPs) were synthesized by ring-opening polymerization of glycosylated N-carboxyanhydride monomer and attached to hydrophobic dendrons at one chain end by "click" reaction to obtain amphiphilic anisotropic macromolecules. We show that by varying polypeptide chain length and dendron generation, an organogel was obtained in dimethylsulfoxide, while nanorods and micellar aggregates were observed in aqueous solutions. Assemblies in water were characterized by electron microscopy and dye encapsulation. Secondary structure of the GP chain was shown to affect the morphology, whereas the chain length of the poly(ethylene glycol) linker between the GP and dendron did not alter rod-like assemblies. Bioactive surface chemistry of these assemblies displaying carbohydrate groups was demonstrated by interaction of mannose-functionalized nanorods with ConA.

Self‐assembly and responsiveness of polypeptide‐based block copolymers: How “Smart” behavior and topological complexity yield unique assembly in aqueous media

“…Recently, Ambade and Sen Gupta studied a complex linear-dendritic ABC terpolymer consisting of a glycopeptide (A), poly(ethylene glycol) (B) and a dendron end cap (C). 117 This complex topology was able to self-assemble into organogels in DMSO, or into micelles and nanotubes in aqueous solution, depending on composition of the component blocks.…”

Responsive organogels formed by supramolecular self assembly of PEG-block-allyl-functionalized racemic polypeptides into β-sheet-driven polymeric ribbons

“…Supramolecular interactions between polypeptide segments 9 have been utilized for the self assembly of peptide-based diblock copolymers into stimuli-responsive vesicles, 5,10,11 micelles, 12–15 hydrogels 16–18 and organogels. 19–22 Organogels made from polypeptides have potential applications as responsive materials in oil recovery, sensing, electrochemistry, drug delivery and as templates for the fabrication of nanostructures.…”

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2011–2012

“…Amino acid glycosides TOF Use of propargyl 1,2-orthoesters as glycosyl donors Amino acid glycosyl carbamates TOF For preparation of nanorods, micelles, and organogels by click chemistry (Pati et al, 2012a) Aminoglycosides TOF For treatment of genetic diseases caused by nonsense mutations (Kandasamy et al, 2012) Amphiphilic disaccharideazobenzene conjugates TOF Helical assembly of azobenzeneconjugated carbohydrate with specific affinity for lectins 2-Anthracenecarboxylates tethered to cyclic tetrasaccharides TOF Diastereocontrolled photocyclodimerization (Fukuhara et al, 2012) Corrole-D-galactose conjugates TOF Synthesis from 5,10,15-tris(pentafluorophenyl) corrole and 1,2:3,4-di-O-isopropylidene--Dgalactopyranose (Cardote et al, 2012) Coumarin triazolylglycosides TOF Synthesized by copper-mediated 1,3-dipolar cycloaddition reactions of carbohydrate azides and 4-alkynylsubstituted coumarins. Luminescence for surface imaging (Nyuchev et al, 2011) Decaprenylphosphorylarabinose analogues TOF (DHB) As arabinofuranosyl donors with mycobacterial arabinosyltransferase 1,2-Diamino-4,5-methylenedioxybenzenelabeled trimer of 2,8-linked sialic acid…”