Topology‐Induced Chiral Amplification and Inversion in Self‐Assembling Dipeptide Films

Abstract

demonstrated the interfacial assembly of the diphenylalanine peptide into nanoarrays by physical vapor deposition or solvent vapor annealing, [7][8][9] which can be used for the fabrication of nanodevice for power generation, [10] electrochemical sensing, optics, and synthetic templates. Stupp et al. demonstrated the X-raytriggered long-range ordering of nanofilaments assembled by highly negatively charged peptide nanofilaments, [11] and they demonstrated that the shear force can also be used to direct the alignment of the selfassembled nanofibrils, [12] which has promising applications in tissue engineering.Chirality is one of the fundamental structural features during peptide selfassembly. Up to now, a wide variety of chiral nanostructures can be assembled by peptides with unique chemical and physical functions. [13][14][15][16][17][18] Recently, simple di-or tripeptides were shown to self-assemble into long-range-ordered nanohelical arrays by water vapor annealing of the amorphous peptide film, which showed great promising applications in chiroptics and catalysis. [19,20] However, the detailed mechanism for the formation of such functional long-range-ordered chiral nanostructures is still unclear.Controlling the topology defects (dislocations, grain boundaries, etc.) during crystal growth has been used to synthesize long-range-ordered twisted structures, [21,22] such as zinc oxide nanohelices [23] and lead sulfide "pine trees." [24] Recently, Kahr et al. demonstrated that the incorporation of molecular additives into organic crystals leads to geometric frustrations and the formation of banded spherulites, indicating the topologydefects has a great influence on the chiral self-assembly of organic molecules. [22] Based on this, in this work we demonstrate that the formation of long-range-ordered peptide chiral nanostructures can be attributed to the topology-induced phase transition from highly crystalline structures to highly twisted nanostructures with nematic-like ordering. Using the Fc-L F L F peptide and S-(+)-2-methylpiperazine (S-MP) as a model system, [19] we investigated the co-assembly of the two components within the confined films at different molar ratio (χ = C diamine /C peptide ) and water vapor temperature (T). When χ = 0.5, which is consistent with the molar ratio in the singlecrystal structure of Fc-L F L F and S-MP (Figure 1a), [19] the amorphous film containing Fc-L F L F and S-MP will transform rapidly into aligned large microcrystals after water vapor annealing treatment. However, if χ is not 0.5 within the self-assembling

Self-assembly of Fibonacci number spirals in amyloid-like nanofibril films

“…4g), indicating a similar molecule arrangement within the polymorphic peptide assemblies. The distinct diameter, length, and handedness of the self-assembled nanohelices can be attributed to the different surface charges and electrostatic interactions of the twisted peptide β-sheets with the increase of χ values (see discussion in the Supplementary information and Figs S14 and S15) [31][32][33].…”

Biomimetic Self-Assembled Chiral Inorganic Nanomaterials: A New Strategy for Solving Medical Problems

“…Such advantages capitalize on the effects of chiral self-assembly, which impact basic cellular behaviors, such as cell adhesion and proliferation, the differentiation-induction of stem cells, and the regulation of tumor cell fates [ 24 , 25 ]. Various forms of chiral self-assembly, including simple structures and the complex assembly of topologies, have shown surprising potential in the field of biomedical science [ 26 ]. Here, we review these chiral self-assembled structures at different scales and morphologies as obtained by diversified synthetic methods, and we outline their distinctive synthetic approaches.…”

On-Demand Dynamic Chirality Selection in Flower Corolla-like Micropillar Arrays

“…8−10 Subsequently, at a supramolecular level, nanostructures undergo chiral inversion through self-assembly depending on the solvents, 11 temperature, 12 and molar ratio of the components. 13 For achiral materials that cannot spontaneously self-assemble into chiral morphologies, templated synthesis 14,15 has been implemented using cellulose nanocrystals (CNCs) as a template. However, CNC-templated synthesized materials cannot dynamically switch their chirality.…”

“…Typically, S N 2 synthetic routes have been adopted to select chirality in organic chemistry for single molecular chiral inversion, where the chemical constituents of the final products are changed from the initial reactants. − Subsequently, at a supramolecular level, nanostructures undergo chiral inversion through self-assembly depending on the solvents, temperature, and molar ratio of the components . For achiral materials that cannot spontaneously self-assemble into chiral morphologies, templated synthesis , has been implemented using cellulose nanocrystals (CNCs) as a template.…”