Su Xin, Liu Shuaijie, Gong Xuewen, Tong Xiaoyu, Li Lingling, Huo Yehong, Liu Qingxi, Wang Yuehui, Tan Mei-Ling, Li Qi, Zhang Shijin, Ji Wei
Key Laboratory of Biorheological Science and Technology, Ministry of Education, College of Bioengineering, Chongqing University, Chongqing 400044, China.
National Engineering Research Center of Ophthalmology and Optometry, School of Biomedical Engineering, Eye Hospital, Wenzhou Medical University, Wenzhou 325027, China.
J Am Chem Soc. 2025 May 14;147(19):16255-16269. doi: 10.1021/jacs.5c01672. Epub 2025 Apr 30.
Supramolecular co-assembly can modulate the architecture of molecular assemblies, thereby influencing their electromechanical properties. However, the relationship between supramolecular packing and electromechanical response of co-assemblies remains largely unexplored, posing a challenge in designing high-performance bioinspired piezoelectric materials. Herein, we combined experiments and theoretical calculations to systematically explore the regulation of supramolecular packing and electromechanical properties of cyclic -aspartyl--aspartyl (cyclo-DD (LL))-based assemblies through co-assembling with pyridine derivatives. Crystal structures indicated that intermolecular hydrogen bonding between the carboxyl group of the cyclic dipeptide and the pyridine ring resulted in a markedly different molecular organizations and packing modes of co-assemblies. Density functional theory calculations revealed that increasing the molecular length of the pyridine derivatives enhanced the polarization effect and piezoelectric response of the cyclo-DD (LL)-based co-assemblies due to the reduced structural symmetry. Notably, the maximum piezoelectric coefficient of the cyclo-DD (LL)/4,4'-trimethylenedipyridine (TDP) co-assembly was predicted to be 140.8 pC/N, representing the highest value among peptide-based co-assemblies. Furthermore, cyclo-DD (LL)/TDP co-assembly based piezoelectric nanogenerator could generate stable open-circuit voltages over 3 V under an applied mechanical force of 50 N. For the first time, peptide-based co-assemblies were utilized as active piezoelectric materials to successfully power a display screen. Moreover, the effect of chirality on the piezoelectricity of cyclic dipeptide-based co-assemblies was investigated. This work presents an effective co-assembly strategy to manipulate the piezoelectric response of bioinspired cyclic dipeptide-based assemblies, advancing the development of high-performance piezoelectric molecular materials for sustainable energy harvesting systems.
超分子共组装可以调节分子组装体的结构，从而影响其机电性能。然而，共组装体的超分子堆积与机电响应之间的关系在很大程度上仍未被探索，这给设计高性能生物启发型压电材料带来了挑战。在此，我们结合实验和理论计算，通过与吡啶衍生物共组装，系统地探索了基于环 - 天冬氨酰 - 天冬氨酰（环 - DD(LL)）的组装体的超分子堆积和机电性能的调控。晶体结构表明，环二肽的羧基与吡啶环之间的分子间氢键导致了共组装体显著不同的分子组织和堆积模式。密度泛函理论计算表明，由于结构对称性降低，增加吡啶衍生物的分子长度增强了基于环 - DD(LL)的共组装体的极化效应和压电响应。值得注意的是，环 - DD(LL)/4,4'-三亚甲基二吡啶（TDP）共组装体的最大压电系数预计为140.8 pC/N，代表了基于肽的共组装体中的最高值。此外，基于环 - DD(LL)/TDP共组装体的压电纳米发电机在50 N的外加机械力下可产生超过3 V的稳定开路电压。首次将基于肽的共组装体用作活性压电材料成功为显示屏供电。此外，还研究了手性对基于环二肽的共组装体压电性的影响。这项工作提出了一种有效的共组装策略来操纵生物启发型基于环二肽的组装体的压电响应，推动了用于可持续能量收集系统的高性能压电分子材料的发展。
