Expanding the Structural Diversity and Functional Scope of Diphenylalanine-Based Peptide Architectures by Hierarchical Coassembly

Abstract

Modulation of the structural diversity of diphenylalanine-based assemblies by molecular modification and solvent alteration has been extensively explored for bio- and nanotechnology. However, regulation of the structural transition of assemblies based on this minimal building block into tunable supramolecular nanostructures and further construction of smart supramolecular materials with multiple responsiveness are still an unmet need. Coassembly, the tactic employed by natural systems to expand the architectural space, has been rarely explored. Herein, we present a coassembly approach to investigate the morphology manipulation of assemblies formed by N-terminally capped diphenylalanine by mixing with various bipyridine derivatives through intermolecular hydrogen bonding. The coassembly-induced structural diversity is fully studied by a set of biophysical techniques and computational simulations. Moreover, multiple-responsive two-component supramolecular gels are constructed through the incorporation of functional bipyridine molecules into the coassemblies. This study not only depicts the coassembly strategy to manipulate the hierarchical nanoarchitecture and morphology transition of diphenylalanine-based assemblies by supramolecular interactions but also promotes the rational design and development of smart hydrogel-based biomaterials responsive to various external stimuli.

Peptide-Based Low Molecular Weight Photosensitive Supramolecular Gelators

“…In view of light-responsive supramolecular gels, azobenzene [ 55 , 85 , 86 , 87 , 88 ], arylazopyrozole [ 89 , 90 , 91 ], benzoylhydrozone [ 92 , 93 ], stilbene [ 60 , 94 ], etc., are more frequently used photoisomerizable molecules that switch between trans - and cis -isomeric forms under the illumination of light ( Figure 1 ). Spiropyran [ 24 , 78 , 80 ] is another critical photo-sensitive unit for light-induced ring-opening and closing behavior.…”

“…Additionally, peptides are well-known for their smaller size (length ranging from 10 to 15 amino acids), even smaller than antibodies, and they are less immunogenic and highly stable in physiological conditions, making them a reliable candidate for conjugation with various kinds of nano-carriers for biological application [ 46 ]. Finally, peptides are well-known for their co-assembling and co-aggregating propensity with a wide range of molecular entities such as other peptide sequences, proteins, polymers, drug molecules, inorganic and other molecules [ 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 ]. Co-assembly can occur at the molecular level in mainly four different ways, viz.…”

“…(a) cooperative co-assembly, (b) self-sorting (or orthogonal co-assembly), (c) random co-assembly, and (d) destructive co-assembly [ 50 ]. These newly generated multicomponent co-assembled systems give access to tailored features, enhanced mechanical and architectural scope, desired morphology, improved bioavailability, and functional complexity with emergent behavior [ 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 ]. In fact, in recent years, a considerable amount of effort have been dedicated in the direction of designing peptide-based multicomponent systems decorated with desired structures, properties, and functions with multitasking abilityies via co-assembly, which is difficult for a monocomponent peptide assembly to realize [ 48 , 57 , 58 , 59 , 60 , 61 ].…”

Unraveling Molecular Assembly and Tracking Lipid Droplets Dynamics using Fluorescent Phenanthroimidazole Derivatives

“…3,[10][11][12][13][14][15][16][17][18] A range of materials has been developed through the tiny change in molecular structures like single atom alteration, side-chain modifications, etc. [19][20][21][22][23][24] However, the fundamental understanding of the dynamics of self-assembly to tune the task-specific functions of molecular materials remains a challenge. The molecular assembly process has a great impact on the size and shape of the aggregate structures and can be tuned through the variation of the local environments like polarity, the viscosity of the medium, and external stimuli like pH, temperature, and light.…”

Fatty Acids/Tetraphenylethylene Conjugates: Hybrid AIEgens for the Preparation of Peptide-Based Supramolecular Gels

“…Peptides are indeed able to organize themselves into ordered structures and are widely exploited in the development of smart materials ( Clerici et al, 2016 ; Fuertes et al, 2017 ; Gagni et al, 2019 ; Banerjee and Hamley, 2020 ; Locarno et al, 2020 ; Vaghi et al, 2020 ; Varanko et al, 2020 ; Bucci et al, 2021a ; Bucci et al, 2021b ; Surís-Valls et al, 2022 ) and supramolecular gels ( Makam and Gazit, 2018 ; Jain and Roy, 2020 ; Tsutsumi et al, 2021 ; Kurbasic et al, 2022 ). Ultra-short peptides derived from natural proteins, such as amyloidogenic ones, have been investigated, the phenylalanine dipeptide being the most exploited motif ( Diaferia et al, 2019 ; Bucci et al, 2020 ; Gil et al, 2020 ; Ji et al, 2021 ; Criado-Gonzalez et al, 2022 ). Here, we selected the IKVAV sequence derived from laminin glycoprotein, one of the major components of the basement membrane ( Patel et al, 2019 ), to be functionalized with the developed FA/TPEs conjugates.…”