Tiwari Nitin S, Merkus Koen, van der Schoot Paul
Department of Applied Physics, Eindhoven University of Technology, P.O. Box 513, 5600 MB, Eindhoven, The Netherlands.
Institute for Theoretical Physics, Utrecht University, 3584 CE, Utrecht, The Netherlands.
Eur Phys J E Soft Matter. 2015 Sep;38(9):105. doi: 10.1140/epje/i2015-15105-5. Epub 2015 Sep 29.
Although pathway-specific kinetic theories are fundamentally important to describe and understand reversible polymerisation kinetics, they come in principle at a cost of having a large number of system-specific parameters. Here, we construct a dynamical Landau theory to describe the kinetics of activated linear supramolecular self-assembly, which drastically reduces the number of parameters and still describes most of the interesting and generic behavior of the system in hand. This phenomenological approach hinges on the fact that if nucleated, the polymerisation transition resembles a phase transition. We are able to describe hysteresis, overshooting, undershooting and the existence of a lag time before polymerisation takes off, and pinpoint the conditions required for observing these types of phenomenon in the assembly and disassembly kinetics. We argue that the phenomenological kinetic parameter in our theory is a pathway controller, i.e., it controls the relative weights of the molecular pathways through which self-assembly takes place.
尽管特定途径的动力学理论对于描述和理解可逆聚合动力学至关重要，但原则上它们的代价是具有大量特定于系统的参数。在此，我们构建了一个动力学朗道理论来描述活化线性超分子自组装的动力学，这极大地减少了参数数量，并且仍然能够描述手头系统的大多数有趣且通用的行为。这种唯象学方法基于这样一个事实，即如果发生成核，聚合转变类似于相变。我们能够描述滞后、超调、欠调以及聚合开始前的滞后时间的存在，并确定在组装和解组装动力学中观察到这些类型现象所需的条件。我们认为我们理论中的唯象学动力学参数是一个途径控制器，即它控制自组装发生所通过的分子途径的相对权重。
