Zipper-featured δ-peptide foldamers driven by donor-acceptor interaction.: Design, synthesis, and characterization
Zipper-featured δ-peptide foldamers driven by donor-acceptor interaction.: Design, synthesis, and characterization
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DOI：
10.1021/jo035149i
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发表时间：
2004-01-23
影响因子：
3.6
通讯作者：
Chen, GJ
中科院分区：
文献类型：
--
作者：
Zhao, X;Jia, MX;Chen, GJ
利用富电子的1，5-二氧萘（DAN）与缺电子的均苯四甲酸二酰亚胺（PDI）之间的给体-受体相互作用，诱导形成了一种新型的具有拉链特征的δ-肽折叠体。设计并通过标准液相合成方法制备了七种基于L-鸟氨酸的δ-肽1a-g，其中在肽骨架的两端分别掺入一到三个DNA和PDI单元。1H-1 NMR，LTV-vis，和荧光猝灭的研究表明，所有的δ-肽采取折叠构象在非极性氯仿和极性DMF作为一个结果的分子内的供体-受体之间的相互作用的DAN和PDI单元。具有更多供体-受体相互作用位点的肽骨架的折叠状态变得更加紧凑。变温LTV-vis实验表明，虽然折叠是一个动态过程，但即使在150 ℃的DMF中，折叠状态也能保持。圆二色谱（CD）研究表明，新一代的δ-肽具有相似的折叠模式。一个拉链特征的折叠基序已被提出为新一代的δ-肽折叠体。分子模拟已经为最长的6肽1g产生了两个最稳定的折叠状态，能量差为26.80 kcal/mol。
Donor-acceptor interaction between electron-rich 1,5-dioxynaphthalene (DAN) and electron-deficient pyromellitic diimide (PDI) has been utilized to induce the formation of a new kind of zipper-featured delta-peptide foldamers. Seven L-ornithine-based delta-peptides 1a-g, in which one to three DNA and PDI units are incorporated to the two ends of the peptide backbones, respectively, have been designed and prepared by the standard liquid-phase synthetic method. H-1 NMR, LTV-vis, and fluorescent quenching studies reveal that all the delta-peptides adopt folding conformations in nonpolar chloroform and polar DMF as a result of intramolecular donor-acceptor interaction between the DAN and PDI units. The folding states become more compact for the peptide skeletons possessing more donor-acceptor interacting sites. Variable-temperature LTV-vis experiments indicate that, although the folding is a dynamic process, the folding state can remain even at 150degreesC in DMF. Circular dichroism (CD) investigations reveal that the new generation of delta-peptides have similar folding patterns. A zipper-featured folding motif has been proposed for the new generation of delta-peptide foldamers. Molecular modeling has generated two most stable folding states for the longest 6-peptide 1g, with an energy difference of 26.80 kcal/mol.