Facile synthesis of block copolypeptides of defined architecture
Facile synthesis of block copolypeptides of defined architecture
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DOI：
10.1038/37084
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发表时间：
1997-11-27
期刊：
影响因子：
64.8
通讯作者：
Deming, TJ
中科院分区：
文献类型：
--
作者：
Deming, TJ
许多天然聚合物材料（特别是结构蛋白）在几个长度尺度上显示出结构层次。嵌段共聚物能够自组装成有序的纳米结构（1，2），但其聚合物链的无规卷曲性质通常抑制任何进一步的组织水平。使用具有规则结构的组分，如刚性棒聚合物，可以增加自组装材料的空间组织程度。但是这种聚合物组分的合成通常涉及复杂的反应步骤，其不适合于大规模生产。蛋白质形成有层次的组织结构，其中基本基序通常是α-螺旋卷曲和β-折叠（4）。合成具有明确定义的氨基酸序列的多肽的尝试，其可能采用类似的有组织的结构，已经受到不希望的副反应的困扰（5），所述副反应产生具有宽范围分子量（6-10）的产物，阻碍了明确定义的肽嵌段共聚物（11-17）的形成。在这里，我描述了一种聚合策略，克服了这些困难，通过使用有机镍引发剂，抑制链转移和终止副反应。这种方法可以方便地合成具有明确序列的嵌段共聚肽，这可能会提供新的基于肽的生物材料，在组织工程，药物输送和仿生复合材料的形成具有潜在的应用。
Many natural polymeric materials (particularly structural proteins) display a hierarchy of structure over several length scales. Block copolymers are able to self-assemble into ordered nanostructures(1,2), but the random-coiled nature of their polymer chains usually suppresses any further levels of organization. The use of components with regular structures, such as rigid-rod polymers, can increase the extent of spatial organization in self-assembling materials(3). But the synthesis of such polymeric components typically involves complicated reaction steps that are not suitable for large-scale production. Proteins form hierarchically organized structures in which the fundamental motifs are generally alpha-helical coils and beta-sheets(4). Attempts to synthesize polypeptides with well-defined amino-acid sequences, which might adopt similar organized structures, have been plagued by unwanted side reactions(5) that give rise to products with a wide range of molecular weights(6-10), hampering the formation of well-defined peptide block copolymers(11-17). Here I describe a polymerization strategy that overcomes these difficulties by using organonickel initiators which suppress chain-transfer and termination side reactions. This approach allows the facile synthesis of block copolypeptides with well-defined sequences, which might provide new peptide-based biomaterials with potential applications in tissue engineering, drug delivery and biomimetic composite formation.