Strong and Sustainable Supramolecular Nanofiber Assembling in Acoustic Flow Field

Abstract

Hierarchical assembly of polysaccharides into nanofiber is at the core of generating advanced biomimetic nanomaterials. However, the artificial synthesis of supramolecular nanofiber from polysaccharides remains an open challenge due to their complicated structure, irregular, and strong interaction. Herein, by mimicking the assembly of natural macromolecules in an out‐of‐equilibrium state, supramolecular nanofiber is successfully fabricated from natural polysaccharides through regular and strong interaction, and a high‐energy and oriented flow field. The high energy of ultrasound can surmount the energy landscape of dynamically stable electrostatic interaction among polysaccharides, while the acoustic‐oriented streaming overcomes the disordered arrangement of macromolecules, thus inducing the orderly arrangement of polysaccharide chains to form kinetically stable nanofibers. The kinetically trapped assembly and the resulting structural evolution can be monitored by scattering and imaging experiments, while the microscopic mechanism can be confirmed by theoretical simulation. Mechanically strong, water‐resistant, and humidity stimulus‐responsive bioplastic film can be fabricated from the supramolecular nanofibers. The discoveries provide critical insights into the assembly of polysaccharides into supramolecular nanofibers and open up many possibilities to prepare advanced nanomaterials from natural polysaccharides.

Fast Catalyst-Free Synthesis of Stereoselective Polypeptides via Hierarchical Chiral Assembly

“…It is worth noting that when transitioning to higher power ultrasonic stimulation, the superhelical structure of PEG 113 - b -PZLL 40 is maintained with a broad length range from ∼50 to ∼200 nm (Figure S20). This may be attributed to the disruption of noncovalent interactions by the enhanced sonication. , …”

“…This may be attributed to the disruption of noncovalent interactions by the enhanced sonication. 27,28 For an in-depth understanding of the system, we conducted a systematic study of the assembly by varying DP PZLL . All of the assemblies from diblock copolymers with DP PZLL at 17, 48, and 73 predominantly exhibited right-handed superhelical structures (Figures S21 and 3g).…”

“…While polypeptide assemblies derived from chiral amino acids as fundamental motifs have been reported to be prepared through ringopening polymerization-induced self-assembly (ROPISA) of N-carboxyanhydrides, 25,26 as of our latest knowledge, the precision control over the ROPISA process for generating Ultrasound serves as an energy source to disrupt and homogenize noncovalent interactions such as hydrogen bonding, hydrophobicity, and π−π interactions among molecular components, altering their packing configuration. 27,28 Additionally, ultrasound waves induce the formation of small bubbles owing to the cavitation effect, creating air− water interfaces that facilitate the assembly by minimizing energy barriers. 29 Herein, we employed high-energy ultrasound to implement α-methoxy-ω-amino poly(ethylene glycol) (mPEG-NH 2 )-initiated aqueous ROPISA of ε-benzyloxycarbonyl-L-lysine N-carboxyanhydride (ZLL-NCA) monomers to obtain hierarchical chiral superhelices within merely a few minutes.…”

Guidelines derived from biomineralized tissues for design and construction of high-performance biomimetic materials: from weak to strong

“…The high energy of ultrasound can break the dynamic interactions among building blocks, and the directional flow of sound waves induces building blocks from a disordered distribution to an ordered arrangement. 621 Zhang et al 622 carried out fast (5 min) self-assembly of melamine with trithiocyanuric acid using ultrasound and constructed kelp-like carbon nitride nanosheets. They emphasized the important role of ultrasound in the self-assembly of the precursor.…”