Supramolecular Glycopolymers in Water: A Reversible Route Toward Multivalent Carbohydrate–Lectin Conjugates Using Cucurbit[8]uril

A Facile Route to Viologen Functional Macromolecules through Azide–Alkyne [3+2] Cycloaddition

“…The reactions containing I − salts took a minimum of 140 min for completion to be achieved, as measured by 1 H NMR, whereas with only PF 6 − salts present completion was reached in under 14 min. This is thought to be due to the ability of the iodide anion, unlike the PF 6 − anion, to act as a bridging ligand between copper centers.…”

“…The reactions containing I − salts took a minimum of 140 min for completion to be achieved, as measured by 1 H NMR, whereas with only PF 6 − salts present completion was reached in under 14 min. This is thought to be due to the ability of the iodide anion, unlike the PF 6 − anion, to act as a bridging ligand between copper centers. [ 34 ] Decrease in the copper content also slowed the rate of reaction between these species, in the presence of all PF 6 − counter ions, the reaction is extremely rapid with equimolar concentrations of copper, however, when decreased to 0.25 equivalents the reaction was signifi cantly slower.…”

“…[5][6][7] High endgroup fi delity is equally important in surface modifi cation, for example, for nanoparticle functionalization and the understanding of biosynthesis. [ 8 ] Designed end-group functionality has been achieved through a variety of controlled polymerization methods [9][10][11] through the use of functional initiators.…”

Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization

“…Scherman et al [156] described a sophisticated strategy for the synthesis of a flexible and reversible supramolecular glycopolymer based on cucurbit(8)uril (supramolecular "handcuff") and viologen α-mannoside (Scheme 18). First, 2-naphthol methacrylate M92 was either homopolymerized or copolymerized with fluorescent rhodamine methacrylate M93 in the presence of A33 and CuBr(L2) (toluene, 70 C) to afford a uniform polymer scaffold with M n = 4200-14,100 Da and Đ = 1.04-1.11.…”

Cucurbit[8]uril ternary complexes for biomolecular assemblies in solution and at interfaces

“…46 A tetravalent lectin was used to crosslink the polymeric backbones by multivalent interactions with the mannose ligands. 46 Alternatively, simply mixing CB [6]-grafted hyaluronic acid (CB [6]-HA) with spermidinefunctionalized bioactive peptides resulted in the formation of supramolecular hostguest systems that could be used for in vitro and in vivo studies as shown by Kim and coworkers ( Fig. 1.11a).…”