Wezenberg Sander J, Metselaar Gerald A, Rowan Alan E, Cornelissen Jeroen J L M, Seebach Dieter, Nolte Roeland J M
Institute for Molecules and Materials, Radboud University Nijmegen, Toernooiveld 1, 6525 ED, Nijmegen, The Netherlands.
Chemistry. 2006 Mar 20;12(10):2778-86. doi: 10.1002/chem.200501042.
Helical polymers of isocyanopeptides derived from beta-amino acids have been synthesized and their architectures have been studied in detail. Similar to their alpha-amino acid analogues, the helical conformation in these macromolecules is stabilized by internal hydrogen-bonding arrays along the polymeric backbone. Unexpectedly, the flexibility of the beta-peptide side arms results in a rearrangement of the initial macromolecular architecture, leading to a more stable helical structure possessing a better defined hydrogen-bonding pattern, as was concluded from IR and temperature-dependent circular dichroism studies. Based on these results we propose a dynamic helical model for the beta-amino acid derived polyisocyanopeptides; this model is in contrast to the kinetically stable helical macromolecules that are formed upon polymerization of alpha-amino acid based isocyanopeptides.
已合成了源自β-氨基酸的异氰肽螺旋聚合物,并对其结构进行了详细研究。与它们的α-氨基酸类似物相似,这些大分子中的螺旋构象通过沿聚合物主链的内部氢键阵列得以稳定。出乎意料的是,β-肽侧链的柔韧性导致初始大分子结构发生重排,从而形成具有更明确氢键模式的更稳定螺旋结构,这是通过红外光谱和温度依赖性圆二色性研究得出的结论。基于这些结果我们提出了一个源自β-氨基酸的聚异氰肽的动态螺旋模型;该模型与基于α-氨基酸的异氰肽聚合形成的动力学稳定螺旋大分子形成对比。