Self-Assembled Nanocube-Based Plasmene Nanosheets as Soft Surface-Enhanced Raman Scattering Substrates toward Direct Quantitative Drug Identification on Surfaces

We report on self-assembled nanocube-based plasmene nanosheets as new surface-enhanced Raman scattering (SERS) substrates toward direct identification of a trace amount of drugs sitting on topologically complex real-world surfaces. The uniform nanocube arrays (superlattices) led to low spatial SERS signal variances (∼2%). Unlike conventional SERS substrates which are based on rigid nanostructured metals, our plasmene nanosheets are mechanically soft and optically semitransparent, enabling conformal attachment to real-world solid surfaces such as banknotes for direct SERS identification of drugs. Our plasmene nanosheets were able to detect benzocaine overdose down to a parts-per-billion (ppb) level with an excellent linear relationship (<i>R</i>² > 0.99) between characteristic peak intensity and concentration. On banknote surfaces, a detection limit of ∼0.9 × 10^–6 g/cm² benzocaine could be achieved. Furthermore, a few other drugs could also be identified, even in their binary mixtures with our plasmene nanosheets. Our experimental results clearly show that our plasmene sheets represent a new class of unique SERS substrates, potentially serving as a versatile platform for real-world forensic drug identification

Free-Standing Bilayered Nanoparticle Superlattice Nanosheets with Asymmetric Ionic Transport Behaviors

Natural cell membranes can directionally and selectively regulate the ion transport, which is critical for the functioning of living cells. Here, we report on the fabrication of an artificial membrane based on an asymmetric nanoparticle superlattice bilayered nanosheet, which exhibits similar ion transport characteristics. The superlattice nanosheets were fabricated <i>via</i> a drying-mediated self-assembly of polystyrene-capped gold nanoparticles at the liquid–air interface. By adopting a layer-by-layer assembly process, an asymmetric nanomembrane could be obtained consisting of two nanosheets with different nanoparticle size. The resulting nanomembranes exhibit an asymmetric ion transport behavior, and diode-like current–voltage curves were observed. The asymmetric ion transport is attributed to the cone-like nanochannels formed within the membranes, upon which a simulation map was established to illustrate the relationship between the channel structure and the ionic selectivity, in consistency with our experimental results. Our superlattice nanosheet-based design presents a promising strategy for the fabrication of next-generation smart nanomembranes for rationally and selectively regulating the ion transport even at a large ion flux, with potential applications in a wide range of fields, including biosensor devices, energy conversion, biophotonics, and bioelectronics

Two-Dimensional Bipyramid Plasmonic Nanoparticle Liquid Crystalline Superstructure with Four Distinct Orientational Packing Orders

Anisotropic plasmonic nanoparticles have been successfully used as constituent elements for growing ordered nanoparticle arrays. However, orientational control over their spatial ordering remains challenging. Here, we report on a self-assembled two-dimensional (2D) nanoparticle liquid crystalline superstructure (NLCS) from bipyramid gold nanoparticles (BNPs), which showed four distinct orientational packing orders, corresponding to horizontal alignment (H-NLCS), circular arrangement (C-NLCS), slanted alignment (S-NLCS), and vertical alignment (V-NLCS) of constituent particle building elements. These packing orders are characteristic of the unique shape of BNPs because all four packing modes were observed for particles with various sizes. Nevertheless, only H-NLCS and V-NLCS packing orders were observed for the free-standing ordered array nanosheets formed from a drying-mediated self-assembly at the air/water interface of a sessile droplet. This is due to strong surface tension and the absence of particle–substrate interaction. In addition, we found the collective plasmonic coupling properties mainly depend on the packing type, and characteristic coupling peak locations depend on particle sizes. Interestingly, surface-enhanced Raman scattering (SERS) enhancements were heavily dependent on the orientational packing ordering. In particular, V-NLCS showed the highest Raman enhancement factor, which was about 77-fold greater than the H-NLCS and about 19-fold greater than C-NLCS. The results presented here reveal the nature and significance of orientational ordering in controlling plasmonic coupling and SERS enhancements of ordered plasmonic nanoparticle arrays

Shape Transformation of Constituent Building Blocks within Self-Assembled Nanosheets and Nano-origami

Self-assembly of nanoparticles represents a simple yet efficient route to synthesize designer materials with unusual properties. However, the previous assembled structures whether by surfactants, polymer, or DNA ligands are “static” or “frozen” building block structures. Here, we report the growth of transformable self-assembled nanosheets which could enable reversible switching between two types of nanosheets and even evolving into diverse third generation nanosheet structures without losing pristine periodicity. Such <i>in situ</i> transformation of nanoparticle building blocks can even be achieved in a free-standing two-dimensional system and three-dimensional origami. The success in such <i>in situ</i> nanocrystal transformation is attributed to robust “plant-cell-wall-like” ion-permeable reactor arrays from densely packed polymer ligands, which spatially define and confine nanoscale nucleation/growth/etching events. Our strategy enables efficient fabrication of nanocrystal nanosheets with programmable building blocks for innovative applications in adaptive tactile metamaterials, optoelectronic devices, and sensors

Large-Scale Self-Assembly and Stretch-Induced Plasmonic Properties of Core–Shell Metal Nanoparticle Superlattice Sheets

We report on a facile interfacial self-assembly approach to fabricate large-scale metal nanoparticle superlattice sheets from nonspherical core–shell nanoparticles, which exhibited reversible plasmonic responses to repeated mechanical stretching. Monodisperse Au@Ag nanocubes (NCs) and Au@Ag nanocuboids (NBs) could be induced to self-assembly at the hexane/water interface, forming uniform superlattices up to at least ∼13 cm² and giving rise to mirror-like reflection. Such large-area mirror-like superlattice sheets exhibited reversible plasmonic responses to external mechanical strains. Under stretching, the dominant plasmonic resonance peak for both NB and NC superlattice sheets shifted to blue, following a power-law function of the applied strain. Interestingly, the power-law exponent (or the decay rate) showed a strong shape dependence, where a faster rate was observed for NB superlattice sheets than that for NC superlattice sheets

Giant Plasmene Nanosheets, Nanoribbons, and Origami

We introduce <i>Plasmene</i> in analogy to grapheneas free-standing, one-particle-thick, superlattice sheets of nanoparticles (“meta-atoms”) from the “plasmonic periodic table”, which has implications in many important research disciplines. Here, we report on a general bottom-up self-assembly approach to fabricate giant plasmene nanosheets (<i>i.e.</i>, plasmene with nanoscale thickness but with macroscopic lateral dimensions) as thin as ∼40 nm and as wide as ∼3 mm, corresponding to an aspect ratio of ∼75 000. In conjunction with top–down lithography, such robust giant nanosheets could be milled into one-dimensional nanoribbons and folded into three-dimensional origami. Both experimental and theoretical studies reveal that our giant plasmene nanosheets are analogues of graphene from the plasmonic nanoparticle family, simultaneously possessing unique structural features and plasmon propagation functionalities