Tandem Catalysis for the Preparation of Cylindrical Polypeptide Brushes
Tandem Catalysis for the Preparation of Cylindrical Polypeptide Brushes
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DOI：
10.1021/ja308620h
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发表时间：
2012-11-28
影响因子：
15
通讯作者：
Deming, Timothy J.
中科院分区：
文献类型：
--
作者：
Rhodes, Allison J.;Deming, Timothy J.
在这里，我们报道了一种通过N-羧酸酐(NCA)聚合合成圆柱形共聚多肽刷子的方法，该方法利用一种新的串联催化方法，允许在直接的一锅程序中制备具有可控链段长度的刷子。不需要中间分离或纯化步骤。为了得到高密度的刷状共肽，我们采用了一种接枝方法，即在NCA的侧链上安装异丙基α-氨基酰胺基团作为掩蔽引发剂。这些基团在钴引发的NCA聚合过程中是惰性的，得到了烯丙氧羰基-α-氨基酰胺取代的多肽主链。然后用镍原位活化异丙基-α-氨基酰胺基团，生成侧链刷状链段生长的引发剂。这种逐步串联的钴和镍催化方法被发现是一种有效的制备高链密度圆柱形共聚肽刷的方法，主链和侧链都可以通过控制链段长度来制备
Here, We report a method for synthesis of cylindrical copolypeptide brushes via N-carboxyanhydride (NCA) polymerization utilizing a new tandem catalysis approach that allows preparation of brushes with Controlled segment lengths in a straightforward, one-pot procedure. requiring no intermediate isolation or purification steps. To obtain high-density brush copolypeptides, we used a "grafting from approach where alloc-alpha-aminoamide groups were installed onto the side chains of NCAs to serve as masked initiators. These groups were inert during cobalt initiated NCA polymerization and gave allyloxycarbonyl-alpha-aminoamide-substituted Polypeptide main chains. The alloc-alpha-aminoamide groups were then activated in situ using nickel to generate initiators for growth of side-chain brush segments. This use of stepwise tandem cobalt and nickel catalysis was found to be an efficient method for preparation of high-chain-density, cylindrical copolypeptide brushes, where both the main chains and side chains can be prepared with controlled segment lengths