Department of Materials Science and Engineering, University of Delaware, Newark, Delaware 19716, USA.
Soft Matter. 2018 Jul 4;14(26):5488-5496. doi: 10.1039/c8sm00435h.
Coiled-coil peptides have proven useful in a range of materials applications ranging from the formation of well-defined fibrils to responsive hydrogels. The ability to design from first principles their oligomerization and subsequent higher order assembly offers their expanded use in producing new materials. Toward these ends, homo-tetrameric, antiparallel, coiled-coil, peptide bundles have been designed computationally, synthesized via solid-phase methods, and their solution behavior characterized. Two different bundle-forming peptides were designed and examined. Within the targeted coiled coil structure, both bundles contained the same hydrophobic core residues. However, different exterior residues on the two different designs yielded sequences with different distributions of charged residues and two different expected isoelectric points of pI 4.4 and pI 10.5. Both coiled-coil bundles were extremely stable with respect to temperature (Tm > 80 C) and remained soluble in solution even at high (millimolar) peptide concentrations. The coiled-coil tetramer was confirmed to be the dominant species in solution by analytical sedimentation studies and by small-angle neutron scattering, where the scattering form factor is well represented by a cylinder model with the dimensions of the targeted coiled coil. At high concentrations (5-15 mM), evidence of interbundle structure was observed via neutron scattering. At these concentrations, the synthetic bundles form soluble aggregates, and interbundle distances can be determined via a structure factor fit to scattering data. The data support the successful design of robust coiled-coil bundles. Despite their different sequences, each sequence forms loosely associated but soluble aggregates of the bundles, suggesting similar dissociated states for each. The behavior of the dispersed bundles is similar to that observed for natural proteins.
螺旋肽在各种材料应用中已被证明是有用的,范围从形成定义明确的原纤维到响应性水凝胶。从第一性原理设计其低聚物化和随后的高级组装的能力为生产新材料提供了其更广泛的用途。为此,通过计算设计了同型四聚体、反平行、螺旋肽束,并通过固相方法合成,并对其溶液行为进行了表征。设计并检查了两种不同的束形成肽。在目标螺旋线圈结构内,两个束都包含相同的疏水性核心残基。然而,两个不同设计中不同的外部残基导致序列具有不同的电荷残基分布和两个不同的预期等电点 pI 4.4 和 pI 10.5。两个螺旋肽束在温度(Tm > 80°C)方面都非常稳定,即使在高(毫摩尔)肽浓度下也保持在溶液中溶解。通过分析沉降研究和小角中子散射证实了螺旋四聚体是溶液中的主要物种,其中散射形式因子很好地由具有目标螺旋线圈尺寸的圆柱模型表示。在高浓度(5-15 mM)下,通过中子散射观察到束间结构的证据。在这些浓度下,合成束形成可溶的聚集体,并且可以通过结构因子拟合散射数据来确定束间距离。数据支持成功设计出稳定的螺旋肽束。尽管它们的序列不同,但每个序列都形成松散结合但可溶的束聚集体,表明每个序列都具有相似的解离状态。分散束的行为类似于天然蛋白质的观察结果。