title: Sequence-Controlled Glycopolymers via Step-Growth Polymerization of Precision Glycomacromolecules for Lectin Receptor Clustering.
abstract: A versatile approach for the synthesis of sequence-controlled multiblock copolymers, using a combination of solid phase synthesis and step-growth polymerization by photoinduced thiol-ene coupling (TEC) is presented. Following this strategy, a series of sequence-controlled glycopolymers is derived from the polymerization of a hydrophilic spacer macromonomer and different glycomacromonomers bearing between one to five α-d-Mannose (Man) ligands. Through the solid phase assembly of the macromonomers, the number and positioning of spacer and sugar moieties is controlled and translates into the sequence-control of the final polymer. A maximum M̅nof 16 kDa, corresponding to a X̅nof 10, for the applied macromonomers is accessible with optimized polymerization conditions. The binding behavior of the resulting multiblock glycopolymers toward the model lectin Concanavalin A (ConA) is studied via turbidity assays and surface plasmon resonance (SPR) measurements, comparing the ability of precision glycomacromolecules and glycopolymers to bind to and cross-link ConA in dependence of the number of sugar moieties and overall molecular weight. The results show that there is a clear correlation between number of Man ligands and Con A binding and clustering, whereas the length of the glycooligomer- or polymer backbone seems to have no effect.
authors.affiliation: Institute of Organic and Macromolecular Chemistry, Heinrich-Heine-University Düsseldorf , Universitätsstraße 1, 40225 Düsseldorf, Germany.
authors.forename: Christoph
authors.initials: C
authors.lastname: Gerke
authors.affiliation: Institute of Organic and Macromolecular Chemistry, Heinrich-Heine-University Düsseldorf , Universitätsstraße 1, 40225 Düsseldorf, Germany.
authors.forename: Morten F
authors.identifier: 0000-0001-5416-7429
authors.initials: MF
authors.lastname: Ebbesen
authors.affiliation: Institute of Organic and Macromolecular Chemistry, Heinrich-Heine-University Düsseldorf , Universitätsstraße 1, 40225 Düsseldorf, Germany.
authors.forename: Dennis
authors.initials: D
authors.lastname: Jansen
authors.affiliation: Institute of Organic and Macromolecular Chemistry, Heinrich-Heine-University Düsseldorf , Universitätsstraße 1, 40225 Düsseldorf, Germany.
authors.forename: Sophia
authors.initials: S
authors.lastname: Boden
authors.affiliation: Institute of Organic and Macromolecular Chemistry, Heinrich-Heine-University Düsseldorf , Universitätsstraße 1, 40225 Düsseldorf, Germany.
authors.forename: Tanja
authors.initials: T
authors.lastname: Freichel
authors.affiliation: Institute of Organic and Macromolecular Chemistry, Heinrich-Heine-University Düsseldorf , Universitätsstraße 1, 40225 Düsseldorf, Germany.
authors.forename: Laura
authors.identifier: 0000-0003-0115-6405
authors.initials: L
authors.lastname: Hartmann
mesh_terms: D016000:Cluster Analysis; D003208:Concanavalin A / Q000737:chemistry; D037102:Lectins / Q000737:chemistry*; D008024:Ligands; D008358:Mannose / Q000737:chemistry*; D008970:Molecular Weight; D058105:Polymerization; D011108:Polymers / Q000737:chemistry*; D020349:Surface Plasmon Resonance
chemical_list: D037102:Lectins; D008024:Ligands; D011108:Polymers; D003208:Concanavalin A; D008358:Mannose