Petryczkiewicz Kamil D, Kootstra Johanan, Le Cacheux Maëlle, Tsygankov Aleksei, Sneep Jan L, Ter Harmsel Matthijs, Harutyunyan Syuzanna R
Stratingh Institute for Chemistry, University of Groningen, Groningen 9747 AG, The Netherlands.
J Am Chem Soc. 2025 Jul 2;147(26):22883-22891. doi: 10.1021/jacs.5c05460. Epub 2025 Jun 17.
Chemical oscillations play a fundamental role in biological systems, yet their synthetic counterparts remain challenging to implement with functional outputs. Here, we report a piperidine-based chemical oscillator that autonomously drives periodic cleavage of a [2]rotaxane carrier, leading to controlled cargo release. The system operates through self-sustained oscillations, triggering rotaxane cleavage and the release of a crown ether cargo. Crown ethers were selected for their reactivity distinct from piperidine, while Fmoc-protected benzylamine rotaxane structures allowed for straightforward carrier modification. For all tested carriers, a piperidine pulse is present and occurs simultaneously with carrier cleavage, yielding up to 95% cargo release. Under flow conditions, periodic cargo release was sustained without extensive reoptimization, demonstrating the robustness of the system. Additionally, by adjusting space velocity, trigger concentration, and inhibitor levels, the oscillation period was varied by up to 2.5 h, with cargo release amplitude changing more than 3-fold. This work demonstrates the potential of catalytic oscillators to regulate downstream processes, paving the way toward construction of complex dynamic chemical systems.
化学振荡在生物系统中起着基础性作用，然而其合成对应物要实现功能输出仍具有挑战性。在此，我们报道了一种基于哌啶的化学振荡器，它能自主驱动[2]轮烷载体的周期性裂解，从而实现对货物释放的控制。该系统通过自持振荡运行，触发轮烷裂解并释放冠醚货物。选择冠醚是因其与哌啶具有不同的反应性，而芴甲氧羰基（Fmoc）保护的苄胺轮烷结构便于对载体进行直接修饰。对于所有测试的载体，都存在哌啶脉冲，且与载体裂解同时发生，货物释放率高达95%。在流动条件下，无需大量重新优化就能持续实现周期性货物释放，证明了该系统的稳健性。此外，通过调节空速、触发剂浓度和抑制剂水平，振荡周期变化可达2.5小时，货物释放幅度变化超过3倍。这项工作展示了催化振荡器调节下游过程的潜力，为构建复杂的动态化学系统铺平了道路。
