Generalized Model of Cooperative Covalent Polymerization: Connecting the Supramolecular Binding Interactions with the Catalytic Behavior
Generalized Model of Cooperative Covalent Polymerization: Connecting the Supramolecular Binding Interactions with the Catalytic Behavior
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协同共价聚合的广义模型：将超分子结合相互作用与催化行为联系起来
DOI：
10.1021/acs.macromol.1c02606
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发表时间：
2022
期刊：
影响因子：
5.5
通讯作者：
Lin, Yao
中科院分区：
文献类型：
--
作者：
Fu, Hailin;Baumgartner, Ryan;Song, Ziyuan;Chen, Chongyi;Cheng, Jianjun;Lin, Yao
肌动蛋白和微管蛋白微丝从它们的亚基动态组装在细胞运动、细胞分裂和生物体肌肉功能中是必不可少的。表征这些蛋白质聚合的成核控制生长动力学是由蛋白质亚单位之间的合作和可逆的非共价相互作用促进的。虽然这种生长动力学已经在许多合成分子的超分子聚合中实现，但在共价聚合中很少见，因为单体和聚合物之间的协同结合事件也必须导致聚合的催化。N-羧酸酐单体的开环聚合就是这样一种体系，根据聚合物的结构，它可以产生很大程度的协同性和自加速作用。在这里，我们应用最新的实验数据，引入了一个简单而普遍的共价聚合动力学模型，将类Michaelis-Menten方程引入到速率定律中，显式地描述了单体与不断增长的高分子链的结合。将生长中的高分子链作为一个合作系统和一个具有不同结合事件的原始“酶”来处理，不仅增加了模型的适用性，而且减少了用于描述该系统的变量的数量。将理论预测与具有不同协同性的实验数据进行了比较。将这一简单的动力学模型应用于具有不同协作性的大分子体系，将有助于聚合物化学家在非多肽体系中发现类似的机制，并利用它们来创建天然合作体系的共价类似物。该模型可以扩展到多种情况，包括在合作共价聚合的反应路径中出现额外中间体或竞争反应物的情况。
The dynamic assembly of actin and tubulin microfilaments from their subunits is imperative in enabling cell motility, cell division, and organismal muscle function. The nucleation-controlled growth kinetics that characterizes these protein polymerizations is facilitated by the cooperative and reversible noncovalent interactions of protein subunits. Although this growth kinetics has been realized in the supramolecular polymerization of numerous synthetic molecules, it is rare in covalent polymerizations since a cooperative binding event between a monomer and a polymer must also lead to catalysis of the polymerization. The ring-opening polymerization ofN-carboxyanhydride monomers is one such system that has been shown to result in large degrees of cooperativity and self-acceleration depending on the polymer architecture. Herein, we apply recent experimental data to introduce a simple and generalized kinetic model of cooperative covalent polymerizations, incorporating a Michaelis–Menten-like equation into the rate laws to describe the binding of a monomer to the growing polymer chain explicitly. The treatment of the growing polymer chain as both a cooperative system and as a primitive “enzyme” with a distinct binding event not only increases the applicability of the model but also reduces the number of variables used to describe the system. The theoretical predictions are compared to experimental data with various levels of cooperativity. The application of this simple kinetic model across a broad range of macromolecular architectures with varying levels of cooperativity will help polymer chemists to discover similar mechanisms in nonpolypeptide systems and utilize them to create covalent analogues of natural cooperative systems. The model can be extended to cover a variety of cases in which additional intermediates or competitive reactants occur in the reaction pathway of cooperative covalent polymerization.
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影响因子：
4.4
作者：
Dear, Alexander J.;Meisl, Georg;Knowles, Tuomas P. J.
通讯作者：
Knowles, Tuomas P. J.
DOI：
--
发表时间：
2015
期刊：
影响因子：
--
作者：
宮島大吾;Jiheong Kang;相田卓三
通讯作者：
相田卓三
DOI：
10.1073/pnas.0402488101
发表时间：
2004-05-25
影响因子：
11.1
作者：
Sievers, A;Beringer, M;Wolfenden, R
通讯作者：
Wolfenden, R
影响因子：
12.4
作者：
Dominguez R;Holmes KC
通讯作者：
Holmes KC
影响因子：
16.6
作者：
Song, Ziyuan;Fu, Hailin;Cheng, Jianjun
通讯作者：
Cheng, Jianjun