Department of Chemistry, Technical University of Munich, Lichtenbergstrasse 4, 85748 Garching, Germany.
Institute for Advanced Study, Technical University of Munich, Lichtenbergstrasse 2a, 85748 Garching, Germany.
J Am Chem Soc. 2021 May 26;143(20):7719-7725. doi: 10.1021/jacs.1c01616. Epub 2021 May 12.
In dynamic combinatorial libraries, molecules react with each other reversibly to form intricate networks under thermodynamic control. In biological systems, chemical reaction networks operate under kinetic control by the transduction of chemical energy. We thus introduced the notion of energy transduction, via chemical reaction cycles, to a dynamic combinatorial library. In the library, monomers can be oligomerized, oligomers can be deoligomerized, and oligomers can recombine. Interestingly, we found that the dynamics of the library's components were dominated by transacylation, which is an equilibrium reaction. In contrast, the library's dynamics were dictated by fuel-driven activation, which is a nonequilibrium reaction. Finally, we found that self-assembly can play a large role in affecting the reaction's kinetics via feedback mechanisms. The interplay of the simultaneously operating reactions and feedback mechanisms can result in hysteresis effects in which the outcome of the competition for fuel depends on events that occurred in the past. In future work, we envision diversifying the library by modifying building blocks with catalytically active motifs and information-containing monomers.
在动态组合化学库中，分子在热力学控制下通过可逆反应形成复杂的网络。在生物系统中，化学反应网络通过化学能的转导在动力学控制下运行。因此，我们将能量转导的概念通过化学反应循环引入到动态组合化学库中。在该库中，单体可以聚合，低聚物可以解聚，低聚物可以重新组合。有趣的是，我们发现库中各成分的动力学主要由转酰基作用主导，这是一种平衡反应。相比之下，库的动力学由燃料驱动的激活所决定，这是一种非平衡反应。最后，我们发现自组装可以通过反馈机制在很大程度上影响反应动力学。同时发生的反应和反馈机制的相互作用可能导致滞后效应，其中对燃料的竞争的结果取决于过去发生的事件。在未来的工作中，我们设想通过用具有催化活性的模体和含有信息的单体来修饰构建模块来使文库多样化。
