Mechanotunable Surface Lattice Resonances in the Visible Optical Range by Soft Lithography Templates and Directed Self-Assembly

We demonstrate a novel colloidal self-assembly approach toward obtaining mechanically tunable, cost-efficient, and low-loss plasmonic nanostructures that show pronounced optical anisotropy upon mechanical deformation. Soft lithography and template-assisted colloidal self-assembly are used to fabricate a stretchable periodic square lattice of gold nanoparticles on macroscopic areas. We stress the impact of particle size distribution on the resulting optical properties. To this end, lattices of narrowly distributed particles (∼2% standard deviation in diameter) are compared with those composed of polydisperse ones (∼14% standard deviation). The enhanced particle quality sharpens the collective surface lattice resonances by 40% to achieve a full width at half-maximum as low as 16 nm. This high optical quality approaches the theoretical limit for this system, as revealed by electromagnetic simulations. One hundred stretching cycles demonstrate a reversible transformation from a square to a rectangular lattice, accompanied by polarization-dependent optical properties. On the basis of these findings we envisage the potential applications as strain sensors and mechanically tunable filters. © 2019 American Chemical Society

Direct Observation of Plasmon Band Formation and Delocalization in Quasi-Infinite Nanoparticle Chains

Chains of metallic nanoparticles sustain strongly confined surface plasmons with relatively low dielectric losses. To exploit these properties in applications, such as waveguides, the fabrication of long chains of low disorder and a thorough understanding of the plasmon-mode properties, such as dispersion relations, are indispensable. Here, we use a wrinkled template for directed self-assembly to assemble chains of gold nanoparticles. With this up-scalable method, chain lengths from two particles (140 nm) to 20 particles (1500 nm) and beyond can be fabricated. Electron energy-loss spectroscopy supported by boundary element simulations, finite-difference time-domain, and a simplified dipole coupling model reveal the evolution of a band of plasmonic waveguide modes from degenerated single-particle modes in detail. In striking difference from plasmonic rod-like structures, the plasmon band is confined in excitation energy, which allows light manipulations below the diffraction limit. The non-degenerated surface plasmon modes show suppressed radiative losses for efficient energy propagation over a distance of 1500 nm. © 2019 American Chemical Society

Magnetic and Electric Resonances in Particle-to-Film-Coupled Functional Nanostructures

We investigate the plasmonic coupling of metallic nanoparticles with continuous metal films by studying the effect of the particle-to-film distance, cavity geometry, and particle size. To efficiently screen these parameters, we fabricated a particle-to-film-coupled functional nanostructure for which the particle size and distance vary. We use gold-core/poly­(<i>N</i>-isopropylacrylamide)-shell nanoparticles to self-assemble a monolayer of well-separated plasmonic particles, introduce a gradient in the nanoparticle size by an overgrowth process, and finally add a coupling metal film by evaporation. These assemblies are characterized using surface probing and optical methods to show localized magnetic and electric field enhancement. The results are in agreement with finite-difference time-domain modeling methods and calculations of the effective permeability and permittivity. Finally, we provide a proof of concept for dynamic tuning of the cavity size by swelling of the hydrogel layer. Thus, the tunability of the coupled resonance and the macroscopic self-assembly technique provides access to a cost-efficient library for magnetic and electric resonances

Silver-Overgrowth-Induced Changes in Intrinsic Optical Properties of Gold Nanorods: From Noninvasive Monitoring of Growth Kinetics to Tailoring Internal Mirror Charges

We investigate the effect of surfactant-mediated, asymmetric silver overgrowth of gold nanorods on their intrinsic optical properties. From concentration-dependent experiments, we established a close correlation of the extinction in the UV/vis/NIR frequency range and the morphological transition from gold nanorods to Au@Ag cuboids. Based on this correlation, a generic methodology for <i>in situ</i> monitoring of the evolution of the cuboid morphology was developed and applied in time-dependent experiments. We find that growth rates are sensitive to the substitution of the surfactant headgroup by comparison of benzylhexadecyldimethylammonium chloride (BDAC) with hexadecyltrimethyl­ammonium chloride (CTAC). The time-dependent overgrowth in BDAC proceeds about 1 order of magnitude slower than in CTAC, which allows for higher control during silver overgrowth. Furthermore, silver overgrowth results in a qualitatively novel optical feature: Upon excitation inside the overlap region of the interband transition of gold and intraband of silver, the gold core acts as a retarding element. The much higher damping of the gold core compared to the silver shell in Au@Ag cuboids induces mirror charges at the core/shell interface as shown by electromagnetic simulations. Full control over the kinetic growth process consequently allows for precise tailoring of the resonance wavelengths of both modes. Tailored and asymmetric silver-overgrown gold nanorods are of particular interest for large-scale fabrication of nanoparticles with intrinsic metamaterial properties. These building blocks could furthermore find application in optical sensor technology, light harvesting, and information technology

Xyloglucan from Tropaeolum majus Seeds Induces Cellular Differentiation of Human Keratinocytes by Inhibition of EGFR Phosphorylation and Decreased Activity of Transcription Factor CREB

Xyloglucan XG (molecular weight 462 kDa, 1,4-/1,4,6-(<i>p</i>Glc) linked backbone, side chains of 1-<i>p</i>Xyl, 1,2-<i>p</i>Xyl, 1-<i>p</i>-Gal) was isolated from the seeds of Tropaeolum majus. XG (100 μg/mL) induced terminal cellular differentiation of human keratinocytes, as demonstrated by immunofluorescence staining and Western blot using cytokeratin 10 and involucrin as marker proteins. Differentiation was also induced by XG-derived oligosaccharides (degree of polymerization 7–9). Quantitative real-time polymerase chain reaction (qPCR) revealed the induction of gene expression of typical differentiation markers (cytokeratin, filaggrin, involucrin, loricrin, transglutaminase) in a time-dependent manner. Whole human genome microarray indicated that most of upregulated genes were related to differentiation processes. Microarray findings on selected genes were subsequently confirmed by qPCR. For identification of the molecular target of xyloglucan PAGE of keratinocyte membrane preparations was performed, followed by blotting with fluorescein isothiocyanate-labeled XG. XG interacting proteins were characterized by MS. Peptide fragments of epidermal growth factor receptor (EGFR) and integrin β4 were identified. Subsequent phospho-kinase array indicated that phosphorylation of EGFR and transcription factor cAMP response element-binding protein (CREB) was decreased in the XG-treated cells. Thus, the XG-induced differentiation of keratinocytes is proposed to be mediated by the inhibition of the phosphorylation of EGFR, leading to a dimished CREB activation, which is essential for the activation of cellular differentiation

Macroscopic Strain-Induced Transition from Quasi-infinite Gold Nanoparticle Chains to Defined Plasmonic Oligomers

We investigate the formation of chains of few plasmonic nanoparticlesso-called plasmonic oligomersby strain-induced fragmentation of linear particle assemblies. Detailed investigations of the fragmentation process are conducted by <i>in situ</i> atomic force microscopy and UV–vis–NIR spectroscopy. Based on these experimental results and mechanical simulations computed by the lattice spring model, we propose a formation mechanism that explains the observed decrease of chain polydispersity upon increasing strain and provides experimental guidelines for tailoring chain length distribution. By evaluation of the strain-dependent optical properties, we find a reversible, nonlinear shift of the dominant plasmonic resonance. We could quantitatively explain this feature based on simulations using generalized multiparticle Mie theory (GMMT). Both optical and morphological characterization show that the unstrained sample is dominated by chains with a length above the so-called infinite chain limitabove which optical properties show no dependency on chain lengthwhile during deformation, the average chain length decrease below this limit and chain length distribution becomes more narrow. Since the formation mechanism results in a well-defined, parallel orientation of the oligomers on macroscopic areas, the effect of finite chain length can be studied even using conventional UV–vis–NIR spectroscopy. The scalable fabrication of oriented, linear plasmonic oligomers opens up additional opportunities for strain-dependent optical devices and mechanoplasmonic sensing

Visualizing Single-Cell Secretion Dynamics with Single-Protein Sensitivity

Cellular secretion of proteins into the extracellular environment is an essential mediator of critical biological mechanisms, including cell-to-cell communication, immunological response, targeted delivery, and differentiation. Here, we report a novel methodology that allows for the real-time detection and imaging of single unlabeled proteins that are secreted from individual living cells. This is accomplished via interferometric detection of scattered light (iSCAT) and is demonstrated with Laz388 cells, an Epstein–Barr virus (EBV)-transformed B cell line. We find that single Laz388 cells actively secrete IgG antibodies at a rate of the order of 100 molecules per second. Intriguingly, we also find that other proteins and particles spanning ca. 100 kDa–1 MDa are secreted from the Laz388 cells in tandem with IgG antibody release, likely arising from EBV-related viral proteins. The technique is general and, as we show, can also be applied to studying the lysate of a single cell. Our results establish label-free iSCAT imaging as a powerful tool for studying the real-time exchange between cells and their immediate environment with single-protein sensitivity