Here, we show that aqueous dispersions of inorganic nanoparticles bearing negative surface charges would trigger the chiral assembly of organic radical cations solubilized in organic solvent at the liquid-liquid interface, which consequently produces stable droplets covered by a layer of inorganic/organic chiral nanocomposites. We demonstrate that chirality transfer across the liquid-liquid interface from the chiral organic monomers to the nanoparticle assemblies is realized. Surprisingly, opposite handedness between molecular assemblies and nanoparticle assemblies is determined from both CD and CPL measurements. Moreover, the functionalities of these "chiral" droplets could be further engineered through either a simple mixing or a droplet merging strategy, which enables to produce fluorescent emissive-tunable, magnetic, as well as magnetofluorescent dual-functional droplets.
The transmission efficiency of electromagnetic waves through waveguide bends in a three-dimensional woodpile photonic crystal is investigated experimentally in the microwave regime. A stable technique of field extrapolation is employed to evaluate the coefficient of transmitted waves both for the reference straight waveguide and waveguide bend. We compare and analyze the transmission spectra of a wide variety of bend structures, and find that the multiface mirror scattering effect and cavity resonant effect in the bend zone are two major factors that influence the transmission property of the waveguide bends. A simple picture of the physical mechanism governing the electromagnetic wave transport at the bend zone can be drawn; this allows easier design of high-efficiency waveguide bend structures.
Abstract Nanoscale curvature‐dependent interactions are of paramount importance in biological systems. Here, we report that nanoscale curvature plays an important role in regulating the chirality of self‐assembled nanocomposites from chiral organic molecules and achiral nanoparticles. Specifically, we show that the supramolecular chirality of the nanocomposites markedly depends on the nanoparticle curvature, where small‐sized nanoparticles of high curvature and large‐sized nanoparticles of low curvature lead to nanocomposites with opposite chirality. Quantitative kinetic experiments and molecular dynamics simulations reveal that nanoparticle curvature plays a key role in promoting the pre‐nucleation oligomerization of chiral molecules, which consequently regulates the supramolecular chirality of the nanocomposites. We anticipate that this study will aid in rational design of an artificial cooperative system giving rise to emergent assembling phenomena that can be surprisingly rich and often cannot be understood by studying the conventional noncooperative systems.
Chirality epitomizes the sophistication of chemistry, representing some of its most remarkable achievements. Yet, the precise synthesis of chiral structures from achiral building blocks remains a profound and enduring challenge in synthetic chemistry and materials science. Here, we demonstrate that achiral colloidal nanocrystals, including Au and Ag nanocrystals, can assemble into long-range-ordered helical assemblies with the assistance of chiral molecules. The synchronized aggregation kinetics between colloidal silver or gold nanocrystals and π-conjugated perylene diimide molecules enables the nanocrystals to precisely follow the helical pathways of the molecular assemblies. This results in the formation of helical nanocrystal assemblies extending over tens of micrometers. These helically organized nanocrystals, exhibiting high positional precision, display linear size-dependent chiroptical properties. Furthermore, more intricate helical assemblies, featuring triple, quadruple, and quintuple nanocrystal strands, can be observed in addition to the commonly encountered double helical assemblies. Finally, these helical assemblies, composed of discrete Ag nanocrystals, can fuse into continuous Ag2S helical structures following a sulfidation reaction, ultimately leading to the formation of diverse metal sulfide helices through cation exchange processes.
Nowadays, it is a research hotspot to realize the controllability of polymer crystal structure in polymer nanocomposites. However, polymer crystals induced by two-dimensional filler always exhibit random orientation, which somewhat limit the improvement of physical properties of polymer materials. In the current paper, dynamic Monte Carlo simulations were performed to explore the methods preparing crystals with uniform orientation. Heterogeneous nucleation of deformed polymer loops grafted on two-dimensional filler can induce the appearance of a special nanohybrid shish-kebab (NHSK) structure, in which the two-dimensional filler acts as "shish" and induces the formation of crystals with uniform orientation. The grafted deformed chains are first heterogeneously nucleated on filler surface, and then free chains participate in crystallization, resulting in the formation of the NHSK structure. The NHSK structure can only be formed in the systems with high interfacial interactions at high temperatures or moderate interfacial interactions at moderate temperatures or low interfacial interactions at low temperatures. The method proposed here can be used to achieve the controllability of polymer crystal orientation in experiments.
A large relative anisotropy can be realized in three-dimensional woodpile photonic crystals in the long-wavelength limit. We find that the anisotropy can be tuned. Transition from positive anisotropy to negative anisotropy can be widely achieved.
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