Ahmad Manzoor, Sarkar Susmita, Bhogade Ravindra, Mondal Abhishek, Mondal Debashis, Mondal Jagannath, Talukdar Pinaki
Department of Chemistry, Indian Institute of Science Education and Research Pune, Dr Homi Bhabha Road, Pashan, Pune 411008, Maharashtra, India.
Center for Interdisciplinary Sciences, Tata Institute of Fundamental Research, Hyderabad 500046, Telangana, India.
Nanoscale. 2025 Feb 6;17(6):3145-3151. doi: 10.1039/d4nr01711k.
The transportation of ions across cell membranes is vital in biological functions and is frequently controlled by external triggers like light, ligands, and voltage. Synthetic ion transport systems, particularly those featuring gating mechanisms, have attracted considerable interest. In this research, we engineered self-assembled barrel rosette ion channels using a photoresponsive azobenzene integrated at an allosteric site. Morphological studies verified more effective self-assembly of the form in contrast to the form. The restricted self-assembly of the form can be ascribed to the nonplanar structure of azobenzene moieties, which inhibits favorable π-π stacking interactions. The ion transport studies demonstrated the formation of ion channels by the form with anion antiport as the primary transport mechanism. In contrast, the form exhibited lower efficiency. Based on these observations, dynamically gated ion transport was achieved by employing two sets of electromagnetic radiation at 365 nm and 450 nm, respectively. Molecular dynamics simulation studies demonstrated that the channel formed by assembling monomers exhibited greater stability when compared to the channel formed by monomers. Additionally, the channel was found to recognize and transport chloride effectively.
离子跨细胞膜的运输在生物功能中至关重要，并且常常受光、配体和电压等外部触发因素的控制。合成离子运输系统，尤其是那些具有门控机制的系统，已经引起了相当大的关注。在本研究中，我们利用整合在变构位点的光响应性偶氮苯设计了自组装桶状玫瑰花结离子通道。形态学研究证实，与 形式相比， 形式的自组装更有效。 形式的受限自组装可归因于 偶氮苯部分的非平面结构，这抑制了有利的π-π堆积相互作用。离子运输研究表明， 形式形成了离子通道，其主要运输机制为阴离子反向转运。相比之下， 形式的效率较低。基于这些观察结果，通过分别使用365 nm和450 nm的两组电磁辐射实现了动态门控离子运输。分子动力学模拟研究表明，与由 单体组装形成的通道相比，由 单体组装形成的通道表现出更高的稳定性。此外，发现 通道能够有效识别和运输氯离子。
