Supramolecular Hydrogels with Tunable Chirality for Promising Biomedical Applications

Abstract

Metrics & MoreArticle Recommendations CONSPECTUS: Chirality exits from molecular-level, supramolecular, and nanoscaled helical structures to the macroscopic level in biological life. Among these various levels, as the central structural motifs in living systems (e.g., double helix in DNA, α-helix, β-sheet in proteins), supramolecular helical systems arising from the asymmetrical spatial stacking of molecular units play a crucial role in a wide diversity of biochemical reactions (e.g., gene replication, molecular recognition, ion transport, enzyme catalysis, and so on). However, the importance of supramolecular chirality and its potential biofunctions has not yet been fully explored. Thus, generating chiral assembly to transfer nature's chiral code to artificial biomaterials is expected to be utilized for developing novel functional biomaterials. As one of the most commonly used biomaterials, supramolecular hydrogels have attracted considerable research interest due to their resemblance to the structure and function of the native extracellular matrix (ECM). Therefore, the performance and manipulation of chiral assembled nanoarchitectures in supramolecular hydrogels may provide useful insights into understanding the role of supramolecular chirality in biology.In this Account, recent progress on chiral supramolecular hydrogels is presented, including how to construct and regulate assembled chiral nanostructures in hydrogels with controllable handedness and then use them to develop chiral hydrogels that could be applied in biology, biochemistry, and medicine. First, a brief introduction is provided to present the basic concept related to supramolecular chirality and the importance of supramolecular chirality in living systems. The chiral assemblies in supramolecular hydrogels are strongly driven by noncovalent interactions between molecular building blocks (such as hydrogen bonding, π−π stacking, hydrophobic, and van der Waals interactions). Consequently, the handedness of these chiral assemblies can be regulated by many extra stimuli including solvents, temperature, pH, metal ions, enzymes, and photoirradiation, which is presented in the second section. This manipulation of the chirality of nanoarchitectures in supramolecular hydrogels can result in the development of potential biofunctions. For example, specific supramolecular chirality-induced biological phenomena (such as controlled cell adhesion, proliferation, differentiation, apoptosis, protein adsorption, drug delivery, and antibacterial adhesion) are presented in detail in the third section. Finally, the outlook of open challenges and future developments of this rapidly evolving field is provided. This account that highlights the diverse chirality-dependent biological phenomena not only helps us to understand the importance of chirality in life but also provides new ideas for designing and preparing chiral materials for more bioapplications.

Tunable Mechanical and Optoelectronic Properties of Organic Cocrystals by Unexpected Stacking Transformation from H- to J- and X-Aggregation

“…found the regulation of supramolecular chirality of nanofibrils by the coassembly approach, which showed important effects on the cell adhesion and proliferation in chiral hydrogels. 45 − 48 Inspired by previous studies, we would like to develop organic optoelectronic crystals by very simple building blocks and decipher the relationship between properties and molecular arrangements. Thus, we selected a rigid aromatic molecule, 4,4′-Bpy, as a model and studied its cocrystallization with different acetylated amino acids ( e .…”

Chirality Effects in Peptide Assembly Structures

“…Left-handed matrix formed by L -phenylalanine derivative was conductive for osteogenic lineage, while right-handed matrix formed by its D -analog was conductive for adipogenic lineage ( Wei et al, 2019 ). These different regulatory effects on cells were suggested to be closely related to stereospecific interactions between peptide assemblies and proteins ( Dou et al, 2019 , 2020 ; Wei et al, 2019 ; Sun et al, 2021 ).…”

Chiral Graphene Hybrid Materials: Structures, Properties, and Chiral Applications

“…It has been experimentally proved that biological properties of biomaterials such as cell adhesion and proliferation, protein adsorption, and antibacterial activity all exhibit chirality‐dependency. [ 256–260 ] Biological imaging makes it possible to directly visualize the biological processes at cellular and even subcellular levels within live cells. Multifunctional biosensors have been developed and used to detect and image intracellular biomolecules.…”