Some thoughts about controllable assembly (III): theoretical frameworks and physicochemical foundations of catassembly

<p indent="0mm">Molecular assembly (MA) is an essential approach for creating new materials and generating novel functions through a bottom-up strategy based on various non-covalent synergistic interactions. However, the efficiency, controllability, and functionality of current artificial MA systems are far inferior to those in biological systems. It is essential to develop more efficient and controllable strategies. Among the diverse controllable MA methods, catassembly has emerged as a novel concept that utilizes catassemblers to accelerate and control the MA process. Catassembly is an effective approach with high selectivity and precision for enhancing the complexity and functionality of MA systems. The development of catassembly is still in the early stage, making it particularly important to thoroughly and systematically explore its theoretical foundations and framework. Herein, by comparing the concept, nature, and complexity of catassembly with catalysis, we demonstrate the study of catassembly should be categorized based on its complexity from three perspectives: matter, energy, information, and their synergy. Through delving into these unique principles and characteristics that emerged at the different complexity levels of catassembly, we further lay the groundwork physicochemical foundation and theoretical framework for catassembly beyond self-assembly. Firstly, in the dimension of matter, catassembly demonstrates complexity in terms of multi-components, multi-steps, and multi-pathways. We further elucidated the mechanisms of how catassemblers can serve as “constructors” or “transporters” to control product distribution and accelerate the mass transfer process. These catassemblers feature the optimal concentration and binding constants in catassembly processes. Secondly, the non-equilibrium catassembly systems, which are commonly observed in life science, should be investigated in the integrated dimension of energy and matter. Leveraging theories of nonequilibrium thermodynamics and kinetics, we explore how catassemblers mediate energy transfer and maintain these dissipative structures, and how catassemblers facilitate faster achievement of steady states and control the concentration and lifespan of dissipative structures in non-equilibrium catassembly processes. Finally, for complex dynamic functional catassembly systems, the information dimension is incorporated atop the matter-energy dimension. Inspired by information theory, we demonstrate how catassemblers act as information carriers to control MA processes. In addition, we further discuss how catassemblers mediate signal transmission and quantify the channel capacity of signaling pathways. Furthermore, incorporating concepts from control theory, we reveal catassemblers may serve as “regulators” to mediate the synergy of positive and negative feedback, therefore controlling the robustness and functionality of chemical information networks. A clearer theoretical foundation and framework for catassembly study can be established from these three integrating dimensions of matter, energy, and information. Nevertheless, developing the theoretical framework of catassembly is challenging and requires drawing on advanced concepts and methodologies from multiple disciplines and fields, including artificial intelligence. These endeavors will facilitate the development of MA and material science.