Mechanisms of Biomolecular Self‐Assembly Investigated Through In Situ Observations of Structures and Dynamics

Abstract

Biomolecular self‐assembly of hierarchical materials is a precise and adaptable bottom‐up approach to synthesizing across scales with considerable energy, health, environment, sustainability, and information technology applications. To achieve desired functions in biomaterials, it is essential to directly observe assembly dynamics and structural evolutions that reflect the underlying energy landscape and the assembly mechanism. This review will summarize the current understanding of biomolecular assembly mechanisms based on in situ characterization and discuss the broader significance and achievements of newly gained insights. In addition, we will also introduce how emerging deep learning/machine learning‐based approaches, multiparametric characterization, and high‐throughput methods can boost the development of biomolecular self‐assembly. The objective of this review is to accelerate the development of in situ characterization approaches for biomolecular self‐assembly and to inspire the next generation of biomimetic materials.

Influence of Peptoid Sequence on the Mechanisms and Kinetics of 2D Assembly

“…Two-dimensional (2D) supramolecular materials offer potential advantages in applications ranging from catalysis to energy production and storage, sensing, and biomedicine. − These materials are normally obtained by self-assembly in which the molecules spontaneously arrange themselves into ordered arrays under controlled experimental conditions such as pH and ionic strength, often at solution–solid interfaces where the outcome is dependent on both the solution conditions and the nature of the substrate. − Several kinds of biopolymers (e.g., proteins, peptides, and DNA) have been successfully assembled into 2D materials, and the assembly pathways have been studied in some cases. ,,,− Often, assembly is observed to follow a multistep pathway involving transient metastable states comprised of amorphous particles or liquid-like clusters and may proceed via assembly of oligomeric growth units, rather than through classical nucleation and growth processes that progress through “monomer”-by- “monomer” attachment to ordered nuclei. ,, However, for most biopolymer systems, the 2D assembly mechanism, the controls on assembly kinetics, and, in particular, the dependence of both on biopolymer sequence remain largely unknown and difficult to predict due to the limited number of studies in which assembly has been directly observed and quantified at sufficiently high spatial and temporal resolution. In this study, we begin to fill this gap in understanding by investigating the relationship between molecular sequence and assembly pathway and kinetics for 2D assemblies of peptoids.…”