Complex three-dimensional (3D) structures in biology (e.g., cytoskeletal webs, neural circuits, and vasculature networks) form naturally to provide essential functions in even the most basic forms of life. Compelling opportunities exist for analogous 3D architectures in human-made devices, but design options are constrained by existing capabilities in materials growth and assembly. We report routes to previously inaccessible classes of 3D constructs in advanced materials, including device-grade silicon. The schemes involve geometric transformation of 2D micro/nanostructures into extended 3D layouts by compressive buckling. Demonstrations include experimental and theoretical studies of more than 40 representative geometries, from single and multiple helices, toroids, and conical spirals to structures that resemble spherical baskets, cuboid cages, starbursts, flowers, scaffolds, fences, and frameworks, each with single- and/or multiple-level configurations.
Have you seen the film? Coupling a spray‐coating technique with a facile, low‐cost, efficient and environmentally friendly electrochemical method may realize the controllable synthesis of large‐area and patterned electrochemically reduced graphene oxide films on various conductive and insulating substrates with thicknesses ranging from a single monolayer to several microns (see figure).
We propose an ingenious method for synthesizing cross-linked hollow fluorescent carbon nanoparticles (HFCNs) with green emission by simply mixing acetic acid, water, and diphosphorus pentoxide. This is an automatic method without external heat treatment to rapidly produce large quantities of HFCNs, in contrast to other syntheses of fluorescent carbon nanoparticles that required high temperature, complicated operations, or long reaction times. Characterizations of HFCNs through high-resolution transmission electron microscopy, infrared/Raman spectroscopy, and X-ray diffraction indicate that abundant small oxygenous graphite domains existed and endowed the HFCNs with fluorescent properties. After simple post-treatments, the cross-linked HFCNs can be used for cell-imaging applications. Compared with traditional dyes and CdTe quantum dots, HFCNs are the superior fluorescent bioimaging agent according to their low toxicity, stability, and resistance to photobleaching. The HFCNs were also applied to watermark ink and fluorescent powder, showing their promising potentials for further wide usage.
Assembly of 3D micro/nanostructures in advanced functional materials has important implications across broad areas of technology. Existing approaches are compatible, however, only with narrow classes of materials and/or 3D geometries. This paper introduces ideas for a form of Kirigami that allows precise, mechanically driven assembly of 3D mesostructures of diverse materials from 2D micro/nanomembranes with strategically designed geometries and patterns of cuts. Theoretical and experimental studies demonstrate applicability of the methods across length scales from macro to nano, in materials ranging from monocrystalline silicon to plastic, with levels of topographical complexity that significantly exceed those that can be achieved using other approaches. A broad set of examples includes 3D silicon mesostructures and hybrid nanomembrane-nanoribbon systems, including heterogeneous combinations with polymers and metals, with critical dimensions that range from 100 nm to 30 mm. A 3D mechanically tunable optical transmission window provides an application example of this Kirigami process, enabled by theoretically guided design.Kirigami | three-dimensional assembly | buckling | membranes T hree-dimensional micro/nanostructures are of growing interest (1-10), motivated by their increasingly widespread applications in biomedical devices (11-13), energy storage systems (14-19), photonics and optoelectronics (20-24), microelectromechanical systems (MEMS) (25-27), metamaterials (21,(28)(29)(30)(31)(32), and electronics (33-35). Of the many methods for fabricating such structures, few are compatible with the highest-performance classes of electronic materials, such as monocrystalline inorganic semiconductors, and only a subset of these can operate at high speeds, across length scales, from centimeters to nanometers. For example, although approaches (36-39) that rely on self-actuating materials for programmable shape changes provide access to a wide range of 3D geometries, they apply only to certain types of materials [e.g., gels (36, 37), liquid crystal elastomers (39), and shape memory alloys (38)], generally not directly relevant to high-quality electronics, optoelectronics, or photonics. Techniques that exploit bending/folding of thin plates via the action of residual stresses or capillary effects are, by contrast, naturally compatible with these modern planar technologies, but they are currently most well developed only for certain classes of hollow polyhedral or cylindrical geometries (1, 10, 40-44). Other approaches (45, 46) rely on compressive buckling in narrow ribbons (i.e., structures with lateral aspect ratios of >5:1) or filaments to yield complex 3D structures, but of primary utility in opennetwork mesh type layouts. Attempts to apply this type of scheme to sheets/membranes (i.e., structures with lateral aspect ratios of <5:1) lead to "kink-induced" stress concentrations that cause mechanical fracture. The concepts of Kirigami, an ancient aesthetic pursuit, involve strategically configured arrays of cuts to gui...
Herein graphene oxide/Ag nanoparticle hybrids (GO/PDDA/AgNPs) were fabricated according to a self-assembly procedure. Using the obtained GO/PDDA/AgNPs as SERS substrates, an ultrasensitive and label-free detection of folic acid in water and serum was demonstrated based on the inherent SERS spectra of folic acid. The modified graphene oxide exhibited strong enrichment of folic acid due to the electrostatic interaction, and the self-assembled Ag nanoparticles greatly enhanced the SERS spectra of folic acid, both of which led to an ultrahigh sensitivity. Therefore, although the SERS enhancement of p-ATP on GO/PDDA/AgNPs was weaker than that on Ag nanoparticles, the SERS signals of folic acid on GO/PDDA/AgNPs were much stronger than that on Ag nanoparticles. To improve the detection, the concentration of GO/PDDA/AgNPs was optimized to reduce background of the graphene oxide. The SERS spectra of the folic acid showed that the minimum detected concentration of folic acid in water was as low as 9 nM with a linear response range from 9 to 180 nM. To estimate the feasibility of the detection method based on GO/PDDA/AgNPs for the practical applications, diluted serum containing different concentrations of folic acid was taken as real samples. It was established that the sensitivity and the linear range for the folic acid in serum were comparable to that in water. This ultrasensitive and label-free SERS detection of folic acid based on GO/PDDA/AgNPs offers great potential for practical applications of medicine and biotechnology.
SERS aptasensors for protein recognition based on Au nanoparticles labeled with aptamers and Raman reporters have been developed, which opens a new way for protein recognition of high sensitivity and selectivity.
Recently, metal−molecule−metal junctions have been actively researched due to their potential applications in molecular electronics, and probing the structure of the molecules in the junctions is crucial for understanding electron-transfer properties. In this paper, self-assembled monolayers (SAMs) of p-aminothiophenol (p-ATP) are formed on a smooth macroscopic gold and silver surface, and colloidal silver nanoplates (∼100 nm edge length and 12 nm thickness) are assembled onto the SAM surface to form the silver nanoplates−molecule−gold (silver) junctions for the first time. The resulting silver nanoplates−molecules−gold (silver) structures are studied with surface enhanced Raman scattering (SERS) at 514.5, 794.4, and 1064 nm excitations, respectively. Initially, there is very weak Raman signal of p-ATP on the smooth macroscopic gold and silver substrates, respectively, but Raman spectra are considerably enhanced by the presence of the silver nanoplates, which is due to the strong electromagnetic coupling between the localized surface plasmon (LSP) of silver nanoplates and the surface plasmon polariton (SPP) of the smooth gold and silver, respectively, so-called LSP−SPP coupling. The Raman spectra obtained are compared with that obtained on silver nanoplates deposited on glass at the specific excitation wavelengths. It was found that the enhancement factor (EF) of the junctions to the probe molecule is 3−9 times larger than that at silver nanoplates deposited on glass, indicating great potential in the research of molecular electronic device and biology by SERS.
Mercury which is a very important pollutant has drawn significant attention in recent research. So far, among the various detection methods, the strategies based on surface-enhanced Raman scattering (SERS) are quite attractive because of the high sensitivity, and especially as it is reported that Hg(2+) can be directly detected by SERS without tagging. However, the procedure for the direct SERS detection of mercury is still unclear with little experimental evidence, limiting further development of Hg(2+) detection by SERS. Herein, we performed a simple method based on SERS for the detection of mercury ions in water without tagging. It is established that in only 2 min, low concentration of Hg(2+) can be recognized based on the decrease of SERS intensity. The detection procedure is investigated by multiple characterizations and the mechanism proven by the obtained data provides a practical way to further improve the sensitivity of the SERS detection. It is demonstrated that the interaction between Hg(2+) and Ag nanoparticles (Ag NPs) could occur in a short time, which includes the complexation of Hg(2+) with citrate and the formation of amalgam due to the reduction of Hg(2+). This interaction influences the surface plasmon resonance (SPR) property of Ag NPs and thereby decays the electromagnetic enhancement of Ag NPs; meanwhile the interaction also causes the zeta potential decrease of Ag NPs and accordingly affects the adsorption of Raman reporter molecules on the surface of Ag NPs. Therefore, the weakness of SERS intensity in the presence of Hg(2+) should be mainly attributed to the interaction between Hg(2+) and Ag NPs. From the mechanism demonstrated, it can be speculated that using fewer Ag NPs in the detection could improve the sensitivity, because at low Hg(2+) concentration the interaction becomes stronger since every Ag nanoparticle acts with more Hg(2+) ions. Accordingly, we establish that 90.9 pM (18.2 ppt) Hg(2+) is detected in 18 μM Ag NPs, which is much lower than that in reported papers.
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