Department of Chemistry, University of Massachusetts Lowell, 1 University Ave., Lowell, MA 01854, USA.
Molecules. 2019 Jan 3;24(1):157. doi: 10.3390/molecules24010157.
Glycopolymers have gained increasing importance in investigating glycan-lectin interactions, as drug delivery vehicles and in modulating interactions with proteins. The synthesis of these glycopolymers is still a challenging and rigorous exercise. In this regard, the highly efficient click reaction, copper (I)-catalyzed alkyne-azide cycloaddition, has been widely applied not only for its efficiency but also for its tolerance of the appended carbohydrate groups. However, a significant drawback of this method is the use of the heavy metal catalyst which is difficult to remove completely, and ultimately toxic to biological systems. In this work, we present the synthesis of carbohydrate-grafted glycopolymers utilizing a mild and catalyst-free perfluorophenyl azide (PFPA)-mediated Staudinger reaction. Using this strategy, mannose (Man) and maltoheptaose (MH) were grafted onto the biodegradable poly(lactic acid) (PLA) by stirring a PFAA-functionalized PLA with a phosphine-derivatized Man or MH in DMSO at room temperature within an hour. The glycopolymers were characterized by ¹H-NMR, F-NMR, P-NMR and FTIR.
糖聚合物在研究糖-凝集素相互作用、作为药物输送载体以及调节与蛋白质相互作用方面变得越来越重要。这些糖聚合物的合成仍然是一项具有挑战性和严格的工作。在这方面，高效的点击反应，铜（I）催化的炔烃-叠氮化物环加成反应，不仅因其效率高，而且因其对附加的碳水化合物基团的耐受性而得到了广泛应用。然而，该方法的一个显著缺点是使用重金属催化剂，这种催化剂很难完全去除，最终对生物系统有毒。在这项工作中，我们提出了利用温和的、无催化剂的全氟苯基叠氮化物（PFPA）介导的Staudinger 反应合成糖基接枝糖聚合物。使用这种策略，通过在 DMSO 中将 PFAA 功能化的 PLA 与膦衍生化的 Man 或 MH 在室温下搅拌一个小时，将甘露糖（Man）和麦芽七糖（MH）接枝到可生物降解的聚乳酸（PLA）上。通过 ¹H-NMR、F-NMR、P-NMR 和 FTIR 对糖聚合物进行了表征。
