Center of Micro and Nanochemistry and Engineering, Organische Chemie I, Universität Siegen , Adolf-Reichwein Straße 2, 57068 Siegen, Germany.
J Am Chem Soc. 2017 Mar 29;139(12):4270-4273. doi: 10.1021/jacs.6b12951. Epub 2017 Mar 15.
The nanoswitches 1 and 2 are interdependently linked in so-called network states (NetStates). In NetState I, defined by presence of [Cu(1)] and 2, the organocatalyst N-methylpyrrolidine catalyzes a conjugate addition. Addition of iron(II) ions as an external chemical trigger to NetState I discharges Cu from [Cu(1)]. The liberated copper(I) ion acts as a second messenger and changes the toggling state at nanoswitch 2. The resulting nanoswitch [Cu(2)] captures the catalytically active species from solution and the conjugate addition is turned OFF. Removal of the original trigger reverses the sequence and turns catalysis ON. The ON/OFF catalytic cycle was run three times in situ.
纳米开关 1 和 2 以所谓的网络状态(NetStates)相互依存地连接在一起。在 NetState I 中,[Cu(1)] 和 2 的存在定义了该状态,此时有机催化剂 N-甲基吡咯烷催化了共轭加成。向 NetState I 中添加铁(II)离子作为外部化学触发因素,会将铜从 [Cu(1)] 中释放出来。释放的铜 (I) 离子充当第二信使,并改变纳米开关 2 的切换状态。生成的纳米开关 [Cu(2)] 从溶液中捕获具有催化活性的物种,共轭加成被关闭。去除原始触发因素会逆转反应序列并使催化作用开启。该 ON/OFF 催化循环在现场进行了三次。