Huang Renliang, Wang Yuefei, Qi Wei, Su Rongxin, He Zhimin
School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, People's Republic of China ; State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, People's Republic of China.
State Key Laboratory of Chemical Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, People's Republic of China.
Nanoscale Res Lett. 2014 Dec 3;9(1):653. doi: 10.1186/1556-276X-9-653. eCollection 2014.
Controlling the self-assembly of diphenylalanine peptide (FF) into various nanoarchitectures has received great amounts of attention in recent years. Here, we report the temperature-induced reversible self-assembly of diphenylalanine peptide to microtubes, nanowires, or organogel in different solvents. We also find that the organogel in isopropanol transforms into crystalline flakes or nanowires when the temperature increases. The reversible self-assembly in polar solvents may be mainly controlled by electronic and aromatic interactions between the FF molecules themselves, which is associated with the dissociation equilibrium and significantly influenced by temperature. We found that the organogel in the isopropanol solvent made a unique transition to crystalline structures, a process that is driven by temperature and may be kinetically controlled. During the heating-cooling process, FF preferentially self-assembles to metastable nanofibers and organogel. They further transform to thermodynamically stable crystal structures via molecular rearrangement after introducing an external energy, such as the increasing temperature used in this study. The strategy demonstrated in this study provides an efficient way to controllably fabricate smart, temperature-responsive peptide nanomaterials and enriches the understanding of the growth mechanism of diphenylalanine peptide nanostructures.
近年来,控制二苯基丙氨酸肽(FF)自组装成各种纳米结构受到了广泛关注。在此,我们报道了二苯基丙氨酸肽在不同溶剂中温度诱导的可逆自组装形成微管、纳米线或有机凝胶。我们还发现,异丙醇中的有机凝胶在温度升高时会转变为结晶薄片或纳米线。极性溶剂中的可逆自组装可能主要由FF分子自身之间的电子和芳香相互作用控制,这与解离平衡相关且受温度显著影响。我们发现,异丙醇溶剂中的有机凝胶向晶体结构发生独特转变,这一过程由温度驱动且可能受动力学控制。在加热 - 冷却过程中,FF优先自组装成亚稳态纳米纤维和有机凝胶。在引入外部能量(如本研究中使用的升高温度)后,它们通过分子重排进一步转变为热力学稳定的晶体结构。本研究中展示的策略提供了一种有效方法来可控地制备智能、温度响应性肽纳米材料,并丰富了对二苯基丙氨酸肽纳米结构生长机制的理解。