Debnath Sisir, Roy Sangita, Abul-Haija Yousef M, Frederix Pim W J M, Ramalhete Susana M, Hirst Andrew R, Javid Nadeem, Hunt Neil T, Kelly Sharon M, Angulo Jesús, Khimyak Yaroslav Z, Ulijn Rein V
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL, UK.
Current Address: Department of Chemistry, Serampore College, 9, William Carey Sarani, Serampore, Hooghly, West Bengal, Pin-712201, India.
Chemistry. 2019 Jun 12;25(33):7881-7887. doi: 10.1002/chem.201806281. Epub 2019 May 13.
The possibility of using differential pre-heating prior to supramolecular gelation to control the balance between hydrogen-bonding and aromatic stacking interactions in supramolecular gels and obtain consequent systematic regulation of structure and properties is demonstrated. Using a model aromatic peptide amphiphile, Fmoc-tyrosyl-leucine (Fmoc-YL) and a combination of fluorescence, infrared, circular dichroism and NMR spectroscopy, it is shown that the balance of these interactions can be adjusted by temporary exposure to elevated temperatures in the range 313-365 K, followed by supramolecular locking in the gel state by cooling to room temperature. Distinct regimes can be identified regarding the balance between H-bonding and aromatic stacking interactions, with a transition point at 333 K. Consequently, gels can be obtained with customizable properties, including supramolecular chirality and gel stiffness. The differential supramolecular structures also result in changes in proteolytic stability, highlighting the possibility of obtaining a range of supramolecular architectures from a single molecular structure by simply controlling the pre-assembly temperature.
本文证明了在超分子凝胶化之前使用差异预热来控制超分子凝胶中氢键和芳香堆积相互作用之间的平衡，并由此系统调节结构和性质的可能性。使用模型芳香肽两亲物芴甲氧羰基-酪氨酰-亮氨酸（Fmoc-YL）以及荧光、红外、圆二色和核磁共振光谱等手段，研究表明，通过在313-365 K范围内临时暴露于高温，然后冷却至室温将超分子锁定在凝胶状态，可以调节这些相互作用的平衡。关于氢键和芳香堆积相互作用之间的平衡，可以确定不同的状态，其转变点为333 K。因此，可以获得具有可定制性质的凝胶，包括超分子手性和凝胶刚度。不同的超分子结构还导致蛋白水解稳定性的变化，这突出了通过简单控制预组装温度从单一分子结构获得一系列超分子结构的可能性。
