Institute of Organic and Macromolecular Chemistry, Heinrich-Heine-University Düsseldorf , Universitätsstraße 1, 40225 Düsseldorf, Germany.
Biomacromolecules. 2017 Mar 13;18(3):787-796. doi: 10.1021/acs.biomac.6b01657. Epub 2017 Feb 8.
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 M̅ of 16 kDa, corresponding to a X̅ of 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.
本文提出了一种通过固相合成和光诱导硫醇-烯（TEC）逐步增长聚合相结合来合成序列可控的多嵌段共聚物的通用方法。采用该策略，从亲水性间隔基大分子单体和带有一至五个α-d-甘露糖（Man）配体的不同糖基大分子单体的聚合得到了一系列序列可控的糖聚物。通过大分子单体的固相组装，可以控制间隔基和糖基的数量和位置，并转化为最终聚合物的序列控制。在优化的聚合条件下，可以获得高达 16 kDa 的数均分子量（M̅），对应于 10 的重均分子量（X̅）。通过浊度测定和表面等离子体共振（SPR）测量研究了所得多嵌段糖聚物与模型凝集素伴刀豆球蛋白 A（ConA）的结合行为，比较了精确定向糖大分子和糖聚物结合和交联 ConA 的能力，取决于糖基的数量和总分子量。结果表明，Man 配体的数量与 ConA 结合和聚集有明显的相关性，而糖寡聚物或聚合物主链的长度似乎没有影响。
