Cyclodextrin-Adamantane Host–Guest Interactions on the Surface of Biocompatible Adamantyl-Modified Glycodendrimers

Abstract

A series of adamantyl-modified glycodendrimers (mPPI-Gx-AdaA-C) was prepared in a two-step synthesis using two efficient reactions: (1) urea bond formation from amine and isocyanate and (2) reductive amination. 1H NMR spectroscopy (host guest titration and ROESY experiments) was used to evaluate the graded effect of steric hindrance as a function of the number and type of oligosaccharide molecules and of the number of adamantyl (Ada) units on the complexation with monomeric β-cyclodextrin (β-CD). Glycosylated fourth generation PPIs showing an average substitution in adamantyl groups of 13% were found to interact with β-CD effectively, and were considered as candidates for further complexation studies with a polymeric cyclodextrin derivative (poly-β-CD). The host–guest interaction features of the maltosylated dense shell glycodendrimer along with the low cytotoxicity provided the rational basis for the use of these adamantyl-functionalized glycodendrimers in the design of supramolecular systems potentially useful as healthcare materials.

Noncovalent functionalization of a nanofibrous network with a bio-inspired heavy metal binding peptide

“…17,18 An adamantyl moiety is known to be included and held strongly in cyclodextrin. [19][20][21] Nearly perfect match and strong binding between the cavity of b-cyclodextrin and guest diameter of adamantyl group was showed previously.…”

Supramolecular Glycodendrimer-Based Hybrid Drugs

“…30 In particular, at the same β-CD/Ada ratio the accessibility of Ada moieties decreases with increasing the dendrimer generation and the number of Ada units on the Besides proof of spatial neighborhood of β-CD ring and Ada unit in the inclusion complex by NOESY or ROESY measurements, the complex formation results also in characteristic downfield shifts for the methylene and methine proton signals of the adamantyl group when located in the hydrophobic cavity of the β-CD. The observed chemical shift effect can be related to the molar fraction of complexed Ada units.…”

“…30 Supramolecular Interaction between the Bioactive β-Cyclodextrin Based Guest 1 and the AdamantylModified Glycodendrimers. The host−guest interaction between β-cyclodextrin based compound 1 and adamantyl groups present on the surface of the glycosylated dendrimers was studied by 1 H NMR spectroscopy to prove the possibility to assemble supramolecular complexes in water.…”

“…This value (Δδ max = +0.147 ppm) was taken from our comprehensive study on β-CD−Ada host−guest interactions on the surface of adamantyl-modified dendrimers. 30 Figure 2 depicts the complexation of the Ada moieties of the three glycodendrimers mPPI-Gx-AdaB (x = 3, 4, or 5) at different β-CD/Ada ratios.…”

“…After concentration under reduced pressure, the residue was redissolved in water and precipitated with acetone to obtain a whitish solid (0.051 g, yield 30% Synthesis of the Adamantyl-Modified Glycodendrimers. The synthesis of the adamantyl-modified glycodendrimer mPPI-G3-AdaB was carried out by following the two step general procedure previously used in ref 30 for the synthesis of the glycodendrimers mPPI-G4-AdaB and mPPI-G5-AdaB.…”