Dynamic Self‐Assembly of Homogenous Microcyclic Structures Controlled by a Silver‐Coated Nanopore

The self‐assembly of nanoparticles is a challenging process for organizing precise structures with complicated and ingenious structures. In the past decades, a simple, high‐efficiency, and reproducible self‐assembly method from nanoscale to microscale has been pursued because of the promising and extensive application prospects in bioanalysis, catalysis, photonics, and energy storage. However, microscale self‐assembly still faces big challenges including improving the stability and homogeneity as well as pursuing new assembly methods and templates for the uniform self‐assembly. To address these obstacles, here, a novel silver‐coated nanopore is developed which serves as a template for electrochemically generating microcyclic structures of gold nanoparticles at micrometers with highly homogenous size and remarkable reproducibility. Nanopore‐induced microcyclic structures are further applied to visualize the diffusion profile of ionic flux. Based on this novel strategy, a nanopore could potentially facilitate the delivery of assembled structures for many practical applications including drug delivery, cellular detection, catalysis, and plasmonic sensing.     

Stimuli‐Directed Colorimetric Interconversion of Helical Polymers Accompanied by a Tunable Self‐Assembly Process

Interconversion between extended and bent structures at the pendant groups of a chiral polyene framework [poly(phenylacetylene) with (R)‐(2‐methoxy‐2‐phenylacetyl)glycine residues linked to 4‐vinylanilines] allows the reversible colorimetric transformation from stretched to compressed helical cis‐transoid polyenic structures through manipulation of the flexible spacer. This transformation generates either organogels (stretched helical form) or nanoparticles (compressed helical form) under the control of polar/low polar stimuli respectively and opens the way to the development of new sensors and stimuli‐sensitive materials based on these concepts.     

Reconfigurable Chiral Self‐Assembly of Peptides through Control of Terminal Charges

Self‐assembly of chiral nanostructures is of considerable interest, since the ability to control the chirality of these structures has direct ramifications in biology and materials science. A new approach to design chiral nanostructures from self‐assembly of N‐(9‐fluorenylmethoxycarbonyl)‐protected phenylalanine‐tryptophan‐lysine tripeptides is reported. The terminal charges can induce helical twisting of the assembled β‐sheets, enabling the formation of well‐defined chiral nanostructures. The degree and direction of twisting in the β‐sheets can be precisely tailored through in situ pH and temperature modulations. This enables the assembly of reconfigurable chiral nanomaterials with easily adjustable size and handedness. These results offer new insight into the mechanism of helical twist formation, which may enable the precise assembly of highly dynamical materials with potential applications in biomedicine, chiroptics, and chiral sensing.     

Non‐Equilibrium Self‐Assembly of Monocomponent and Multicomponent Tubular Structures in Rotating Fluids

When suspended in a denser rotating fluid, lighter particles experience a cylindrically symmetric confining potential that drives their crystallization into either monocomponent or unprecedented binary tubular packing. These assemblies form around the fluid's axis of rotation, can be dynamically interconverted (upon accelerating or decelerating the fluid), can exhibit preferred chirality, and can be made permanent by solidifying the fluid. The assembly can be extended to fluids forming multiple concentric interfaces or to systems of bubbles forming both ordered and “gradient” structures within curable polymers.     

Highly Stretchable Superhydrophobic Composite Coating Based on Self‐Adaptive Deformation of Hierarchical Structures

With the rapid development of stretchable electronics, functional textiles, and flexible sensors, water‐proof protection materials are required to be built on various highly flexible substrates. However, maintaining the antiwetting of superhydrophobic surface under stretching is still a big challenge since the hierarchical structures at hybridized micro‐nanoscales are easily damaged following large deformation of the substrates. This study reports a highly stretchable and mechanically stable superhydrophobic surface prepared by a facile spray coating of carbon black/polybutadiene elastomeric composite on a rubber substrate followed by thermal curing. The resulting composite coating can maintain its superhydrophobic property (water contact angle ≈170° and sliding angle <4°) at an extremely large stretching strain of up to 1000% and can withstand 1000 stretching–releasing cycles without losing its superhydrophobic property. Furthermore, the experimental observation and modeling analysis reveal that the stable superhydrophobic properties of the composite coating are attributed to the unique self‐adaptive deformation ability of 3D hierarchical roughness of the composite coating, which delays the Cassie–Wenzel transition of surface wetting. In addition, it is first observed that the damaged coating can automatically recover its superhydrophobicity via a simple stretching treatment without incorporating additional hydrophobic materials.     

Hierarchical Multicomponent Inorganic Metamaterials: Intrinsically Driven Self‐Assembly at the Nanoscale

Increasingly intricate in their composition and structural organization, hierarchical multicomponent metamaterials with nonlinear spatially reconfigurable functionalities challenge the intrinsic constraints of natural materials, revealing tremendous potential for the advancement of biochemistry, nanophotonics, and medicine. Recent breakthroughs in high‐resolution nanofabrication utilizing ultranarrow, precisely controlled ion or laser beams have enabled assembly of architectures of unprecedented structural and functional complexity, yet costly, time‐ and energy‐consuming high‐resolution sequential techniques do not operate effectively at industry‐required scale. Inspired by the fictional Baron Munchausen's fruitless attempt to pull himself up, it is demonstrated that metamaterials can undergo intrinsically driven self‐assembly, metaphorically pulling themselves up into existence. These internal drivers hold a key to unlocking the potential of metamaterials and mapping a new direction for the large‐area, cost‐efficient self‐organized fabrication of practical devices. A systematic exploration of these efforts is presently missing, and the driving forces governing the intrinsically driven self‐assembly are yet to be fully understood. Here, recent progress in the self‐organized formation and self‐propelled growth of complex hierarchical multicomponent metamaterials is reviewed, with emphasis on key principles, salient features, and potential limitations of this family of approaches. Special stress is placed on self‐assembly driven by plasma, current in liquid, ultrasonic, and similar highly energetic effects, which enable self‐directed formation of metamaterials with unique properties and structures.     

Self‐Assembly: I‐Motif Nanospheres: Unusual Self‐Assembly of Long Cytosine Strands (Small 8/2011)

The synthesis and characterization of novel DNA structures based on tetraplex cytosine (C) arrangements, known as i‐motifs or i‐tetraplexes, is reported. Atomic force microscopy (AFM) investigation shows that long C‐strands in mild acidic conditions form compact spherically shaped nanostructures. The DNA nanospheres are characterized by a typical uniform shape and narrow height distribution. Electrostatic force microscopy (EFM) measurements performed on the i‐motif spheres clearly show their electrical polarizability. Further investigations by scanning tunneling microscopy (STM) at ultrahigh vacuum reveals that the structures exhibit an average voltage gap of 1.9 eV, which is narrower than the voltage gap previously measured for poly(dG)–poly(dC) molecules in similar conditions.     

Bionanosphere Lithography via Hierarchical Peptide Self‐Assembly of Aromatic Triphenylalanine

A nanolithographic approach based on hierarchical peptide self‐assembly is presented. An aromatic peptide of N‐(t‐Boc)‐terminated triphenylalanine is designed from a structural motif for the β‐amyloid associated with Alzheimer's disease. This peptide adopts a turnlike conformation with three phenyl rings oriented outward, which mediate intermolecular π–π stacking interactions and eventually facilitate highly crystalline bionanosphere assembly with both thermal and chemical stability. The self‐assembled bionanospheres spontaneously pack into a hexagonal monolayer at the evaporating solvent edge, constituting evaporation‐induced hierarchical self‐assembly. Metal nanoparticle arrays or embossed Si nanoposts could be successfully created from the hexagonal bionanosphere array masks in conjunction with a conventional metal‐evaporation or etching process. Our approach represents a bionanofabrication concept that biomolecular self‐assembly is hierarchically directed to establish a straightforward nanolithography compatible with conventional device‐fabrication processes.