The ingenious design and synthesis of novel macrocycles bring out renewed vigor of supramolecular chemistry in the past decade. As an intriguing class of macrocycles, pillararene and pillararene-based functional materials that are constructed through the noncovalent bond self-assembly approach have been undergoing a rapid growth, benefiting from their unique structures and physiochemical properties. This review elaborates recent significant advances of electrochemical studies based on pillararene systems. Fundamental electrochemical behavior of pillar[n]arene[m]quinone and pillararene-based self-assemblies as well as their applications in electrochemical biosensors are highlighted. In addition, the advantages and functions of pillararene self-assembly systems resulted from the unique molecular architectures are analyzed. Finally, current challenges and future development tendency in this burgeoning field are discussed from the viewpoint of both fundamental research and applications. Overall, this review not only manifests the main development vein of pillararene-based electrochemical systems, but also conquers a solid foundation for their further bioelectrochemical applications.

在过去十年中，新颖的大环化合物的巧妙设计和合成带来了超分子化学的新活力。作为一种有趣的大环化合物，通过非共价键自组装方法构建的基于柱芳烃和基于柱芳烃的功能材料正经历快速发展，这得益于其独特的结构和理化特性。这篇综述阐述了基于柱状芳烃体系的电化学研究的最新重大进展。重点介绍了基于柱[n]芳烃[m]醌和基于柱芳烃的自组装的基本电化学行为及其在电化学生物传感器中的应用。此外，分析了由独特的分子结构产生的柱状芳烃自组装系统的优点和功能。最后，从基础研究和应用的角度探讨了该新兴领域当前的挑战和未来的发展趋势。总的来说，本综述不仅体现了基于柱状芳烃的电化学系统的主要发展脉络，而且还为其进一步的生物电化学应用奠定了坚实的基础。