Kortelainen Minna, Suhonen Aku, Hamza Andrea, Pápai Imre, Nauha Elisa, Yliniemelä-Sipari Sanna, Nissinen Maija, Pihko Petri M
Department of Chemistry, Nanoscience Center, University of Jyväskylä, P.O. Box 35, 40014 JYU (Finland), Fax: (+358) 14-260-2501.
Institute of Organic Chemistry, Research Center for Natural Sciences, Hungarian Academy of Sciences, Magyar Tudósok Körútja 2, 1117, Budapest (Hungary).
Chemistry. 2015 Jun 22;21(26):9493-504. doi: 10.1002/chem.201406521. Epub 2015 May 12.
A series of small, unsymmetrical pyridine-2,6-dicarboxylamide oligoamide foldamers with varying lengths and substituents at the end groups were synthetized to study their conformational properties and folding patterns. The @-type folding pattern resembled the oxyanion-hole motifs of enzymes, but several alternative folding patterns could also be characterized. Computational studies revealed several alternative conformers of nearly equal stability. These folding patterns differed from each other in their intramolecular hydrogen-bonding patterns and aryl-aryl interactions. In the solid state, the foldamers adopted either the globular @-type fold or the more extended S-type conformers, which were very similar to those foldamers obtained computationally. In some cases, the same foldamer molecule could even crystallize into two different folding patterns, thus confirming that the different folding patterns are very close in energy in spite of their completely different shapes. Finally, the best match for the observed NOE interactions in the liquid state was a conformation that matched the computationally characterized helix-type fold.
合成了一系列具有不同长度和端基取代基的小的、不对称的吡啶-2,6-二甲酰胺寡酰胺折叠体，以研究它们的构象性质和折叠模式。@型折叠模式类似于酶的氧负离子洞基序，但也可以表征几种其他的折叠模式。计算研究揭示了几种稳定性几乎相等的替代构象。这些折叠模式在分子内氢键模式和芳基-芳基相互作用方面彼此不同。在固态中，折叠体采用球状@型折叠或更伸展的S型构象，这与通过计算获得的那些折叠体非常相似。在某些情况下，相同的折叠体分子甚至可以结晶成两种不同的折叠模式，从而证实尽管不同的折叠模式形状完全不同，但它们在能量上非常接近。最后，对于在液态中观察到的NOE相互作用的最佳匹配是一种与计算表征的螺旋型折叠相匹配的构象。
