Enhancement of metallo-supramolecular dissociation kinetics in telechelic terpyridine-capped poly(ethylene glycol) assemblies in the semi-dilute regime.
Enhancement of metallo-supramolecular dissociation kinetics in telechelic terpyridine-capped poly(ethylene glycol) assemblies in the semi-dilute regime.
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半稀释状态下遥爪三联吡啶封端的聚乙二醇组件中金属超分子解离动力学的增强
DOI：
10.1039/c9cp03911b
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
S. Seiffert
中科院分区：
文献类型：
--
作者：
W. Schmolke;M. Ahmadi;S. Seiffert
超分子聚合物组件的动力学是由它们的聚合物构建块和它们之间的瞬态键的动力学所控制的。这种化学键被拓扑拥挤所困住，常常导致化学键寿命向延长方向的重整化。相比之下，在本研究中，我们表明，在半稀溶液中的远旋金属超分子聚合物的情况下，这种效应也可以是相反的。我们关注的是在两端被三吡啶结合基序覆盖的线性聚乙二醇，它可以与各种过渡金属离子形成金属配体配位键，从而形成不同长度和结合强度的瞬态金属超分子组装体。振荡剪切流变学测量以及这些样品的力学光谱的理论建模表明，复合物的解离动力学显著增强，这取决于聚合物链段的长度，较长的链段产生更快的解离时间，比自由配合物的解离时间缩短了6个数量级。这一发现表明，聚合物链本身的动态活性导致复杂的不稳定。
The dynamics of supramolecular polymer assemblies is governed by that of their polymeric building blocks and that of the transient bonds between them. Entrapment of such bonds by topological crowding often causes renormalization of the bond lifetimes towards prolonging. In the present study, by contrast, we show that this effect can also be inverse in the case of telechelic metallo-supramolecular polymers in semi-dilute solution. We focus on linear poly(ethylene glycols) capped by terpyridine binding motifs at both ends that can form metal–ligand coordinative bonds with various transition metal ions, thereby creating transient metallo-supramolecular assemblies of varying length and binding strength. Oscillatory shear rheology measurements along with theoretical modelling of the mechanical spectra of these samples reveals a pronounced enhancement of the complex dissociation kinetics that is dependent on the length of the polymeric chain segment, with longer segments yielding faster dissociation times up to six orders of magnitude shorter than described for the free complexes. This finding indicates that the dynamic activity of the polymer chain itself causes complex destabilization.
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影响因子：
5.5
作者：
E. Ruymbeke;D. Vlassopoulos;M. Mierzwa;T. Pakuła;D. Charalabidis;M. Pitsikalis;N. Hadjichristidis
通讯作者：
E. Ruymbeke;D. Vlassopoulos;M. Mierzwa;T. Pakuła;D. Charalabidis;M. Pitsikalis;N. Hadjichristidis
影响因子：
3.3
作者：
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通讯作者：
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影响因子：
3.3
作者：
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通讯作者：
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影响因子：
5
作者：
Czarnecki, Sebastian;Rossow, Torsten;Seiffert, Sebastian
通讯作者：
Seiffert, Sebastian
影响因子：
6.2
作者：
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通讯作者：
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