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金属调控的四态纳米开关控制十一组分体系中的两步顺序催化反应。

A Metalloregulated Four-State Nanoswitch Controls Two-Step Sequential Catalysis in an Eleven-Component System.

机构信息

Center of Micro and Nanochemistry and Engineering, Organische Chemie I, Universität Siegen, Adolf-Reichwein Str. 2, 57068, Siegen, Germany.

出版信息

Angew Chem Int Ed Engl. 2016 Aug 22;55(35):10512-7. doi: 10.1002/anie.201604658. Epub 2016 Jul 20.

DOI:10.1002/anie.201604658
PMID:27436617
Abstract

The nanomechanical switch 1 with its three orthogonal binding motifs-the zinc(II) porphyrin, azaterpyridine, and shielded phenanthroline binding station-is quantitatively and reversibly toggled back and forth between four different switching states by means of addition and removal of appropriate metal-ion inputs. Two of the four switching stages are able to initiate catalytic transformations (ON1, ON2), while the two others shut down any reaction (OFF1, OFF2). Thus, in a cyclic four-state switching process the sequential transformation A+B+C→AB+C→ABC can be controlled, which proceeds stepwise along the switching states OFF1→ON1 (click reaction: A+B→AB)→OFF2→ON2 (Michael addition: AB+C→ABC)→OFF1. Two consecutive cycles of the sequential catalysis were realized without loss in activity in a reaction system with eleven different components.

摘要

具有三个正交结合基序(锌(II)卟啉、氮杂三联吡啶和屏蔽的菲咯啉结合站)的纳米机械开关 1 通过添加和去除适当的金属离子输入,可在四个不同的开关状态之间进行定量和可逆地来回切换。四个开关阶段中的两个能够启动催化转化(ON1、ON2),而另外两个则关闭任何反应(OFF1、OFF2)。因此,在循环的四态切换过程中,可以控制顺序转化 A+B+C→AB+C→ABC,该转化沿着切换状态 OFF1→ON1(点击反应:A+B→AB)→OFF2→ON2(迈克尔加成:AB+C→ABC)→OFF1 逐步进行。在具有十一个不同组分的反应体系中,实现了两个连续的顺序催化循环,而没有活性损失。

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