Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
J Am Chem Soc. 2012 Mar 7;134(9):4112-5. doi: 10.1021/ja3007484. Epub 2012 Feb 27.
Conformation-switchable glycopolypeptides were prepared by the living polymerization of glycosylated L-cysteine-N-carboxyanhydride (glyco-C NCA) monomers. These new monomers were prepared in high yield by coupling of alkene-terminated C-linked glycosides of D-galactose or D-glucose to L-cysteine using thiol-ene "click" chemistry, followed by their conversion to the corresponding glyco-C NCAs. The resulting glycopolypeptides were found to be water-soluble and α-helical in solution. Aqueous oxidation of the side-chain thioether linkages in these polymers to sulfone groups resulted in disruption of the α-helical conformations without loss of water solubility. The ability to switch chain conformation and remain water-soluble is unprecedented in synthetic polymers, and allows new capabilities to control presentation of sugar functionality in subtly different contexts.
通过糖基化 L-半胱氨酸-N-羧酸酐（glyco-C NCA）单体的活性聚合，制备了构象可切换糖肽。这些新的单体是通过烯基封端的 D-半乳糖或 D-葡萄糖的 C 连接糖苷与 L-半胱氨酸用硫醇-烯“点击”化学偶联，然后转化为相应的 glyco-C NCAs 来制备的，产率很高。所得糖肽在溶液中是水溶性和α-螺旋的。这些聚合物中侧链硫醚键的水氧化导致α-螺旋构象的破坏，而不损失其水溶性。在合成聚合物中，能够切换链构象并保持水溶性是前所未有的，这为在略有不同的情况下控制糖功能的呈现提供了新的能力。
