Helium Ion Microscopy and Sectioning of Spider Silk.

Focused ion beams have recently emerged as a powerful tool for ultrastructural imaging of biological samples. In this article, we show that helium ion microscopy (HIM), in combination with ion milling, can be used to visualize the inner structure of both major and minor ampullate silk fibers of the orb-web weaving spider Nephila madagascariensis. The internal nanofibrils were imaged in pristine silk fibers, with little or no damage to the sample structure observed. Furthermore, a method to cut/rupture the fibers using He+ ions combined with internal sample tension is presented. This showed that the stretching and rupturing of spider silk is a highly dynamic process with considerable material reorganization.

Nanoscale imaging of major and minor ampullate silk from the orb-web spider Nephila Madagascariensis.

Spider silk fibres have unique mechanical properties due to their hierarchical structure and the nanoscale organization of their proteins. Novel imaging techniques reveal new insights into the macro- and nanoscopic structure of Major (MAS) and Minor (MiS) Ampullate silk fibres from pristine samples of the orb-web spider Nephila Madagascariensis. Untreated threads were imaged using Coherent Anti-Stokes Raman Scattering and Confocal Microscopy, which revealed an outer lipid layer surrounding an autofluorescent protein core, that is divided into two layers in both fibre types. Helium ion imaging shows the inner fibrils without chemical or mechanical modifications. The fibrils are arranged parallel to the long axis of the fibres with typical spacing between fibrils of 230 nm ± 22 nm in the MAS fibres and 99 nm ± 24 nm in the MiS fibres. Confocal Reflection Fluorescence Depletion (CRFD) microscopy imaged these nano-fibrils through the whole fibre and showed diameters of 145 nm ± 18 nm and 116 nm ± 12 nm for MAS and MiS, respectively. The combined data from HIM and CRFD suggests that the silk fibres consist of multiple nanoscale parallel protein fibrils with crystalline cores oriented along the fibre axes, surrounded by areas with less scattering and more amorphous protein structures.

Marine Algae Incorporated Polylactide Acid Patch: Novel Candidate for Targeting Osteosarcoma Cells without Impairing the Osteoblastic Proliferation.

Biodegradable collagen-based materials have been preferred as scaffolds and grafts for diverse clinical applications in density and orthopedy. Besides the advantages of using such bio-originated materials, the use of collagen matrices increases the risk of infection transmission through the cells or the tissues of the graft/scaffold. In addition, such collagen-based solutions are not counted as economically feasible approaches due to their high production cost. In recent years, incorporation of marine algae in synthetic polymers has been considered as an alternative method for preparation grafts/scaffolds since they represent abundant and cheap source of potential biopolymers. Current work aims to propose a novel composite patch prepared by blending Sargassum vulgare powders (SVP) to polylactide (PLA) as an alternative to the porcine-derived membranes. SVP-PLA composite patches were produced by using a modified solvent casting method. Following detailed material characterization to assess the cytocompatibility, human osteoblasts (HOBs) and osteosarcoma cells (SaOS-2) were seeded on neat PLA and SVP-PLA patches. MTT and BrdU assays indicated a greater cytocompatibility and higher proliferation for HOBs cultured on SVP-PLA composite than for those cultured on neat PLA. SaOS-2 cells cultured on SVP-PLA exhibited a significant decrease in cell proliferation. The composite patch described herein exhibits an antiproliferative effect against SaOS-2 cells without impairing HOBs' adhesion and proliferation.

Photodeposition of Au Nanoclusters for Enhanced Photocatalytic Dye Degradation over TiO2 Thin Film.

Au nanoparticle (NP) decorated heterogeneous TiO2 catalysts are known to be effective in the degradation of various organic pollutants. The photocatalytic performance of such Au-TiO2 structures remarkably depends on the size, morphology, and surface coverage of the Au NPs decorating TiO2. Here we propose an effective way of preparing a highly active Au nanocluster (NC) decorated TiO2 thin film by a novel photodeposition method. By altering the solvent type as well as the illumination time, we achieved well-controlled surface coverage of TiO2 by Au NCs, which directly influences the photocatalytic performance. Here the Au NCs coverage affects both the electron store capacity and the optical absorption of the hybrid Au-TiO2 system. At low surface coverage, 19.2-29.5%, the Au NCs seem to enhance significantly the optical adsorption of TiO2 at UV wavelengths which therefore leads to a higher photocatalytic performance.

Tailoring optical discs for surface plasmon polaritons generation.

The article reports on an optimization of gold submicron structures based on modified recordable blank digital versatile discs for surface plasmon polaritions excitation, mainly in near-infrared region. We have examined internal layers of commercially available DVD+R, DVD-R, DVD+RW and DVD-RW optical discs and we have elaborated a simple, inexpensive approach providing sharp resonances with efficiency reaching 95% for collimated excitation laser beams. We have experimentally and numerically confirmed the SPPs intensity being up to 220 times the intensity of the excitation laser beam. We have also directly measured thermal energy loss accompanying SPPs excitation.

Femtosecond time-resolved photoemission electron microscopy operated at sample illumination from the rear side.

We present an advanced experimental setup for time-resolved photoemission electron microscopy (PEEM) with sub-20 fs resolution, which allows for normal incidence and highly local sample excitation with ultrashort laser pulses. The scheme makes use of a sample rear side illumination geometry that enables us to confine the sample illumination spot to a diameter as small as 6 µm. We demonstrate an operation mode in which the spatiotemporal dynamics following a highly local excitation of the sample is globally probed with a laser pulse illuminating the sample from the front side. Furthermore, we show that the scheme can also be operated in a time-resolved normal incidence two-photon PEEM mode with interferometric resolution, a technique providing a direct and intuitive real-time view onto the propagation of surface plasmon polaritons.

Cauliflower-like CeO2-TiO2 hybrid nanostructures with extreme photocatalytic and self-cleaning properties.

In recent years, heterogeneous photocatalysis has gained enormous interest due to increasing concerns about environmental pollution. Here we propose a facile approach to synthesize cauliflower-like CeO2-TiO2 hybrid structures by magnetron reactive sputtering, exhibiting an extremely high photocatalytic activity. While heating and air-quenching of the sputter deposited TiO2 thin film (first layer) triggered the formation of a nanocrack network, the second heat-treatment led to transformation of the CeO2 film (second layer) into CeO2 nanoclusters (NCs). We attribute the resulting high photocatalytic activity to the confined structure of the CeO2 NCs and the CeO2-TiO2 interface, which allows Ce3+/Ce4+ dynamic shifting. In addition to high photocatalytic activity in an aqueous medium, the prepared CeO2-TiO2 hybrid structures exhibited significant self-cleaning properties in air (non-aqueous).

Formation of Si Nanorods and Discrete Nanophases by Axial Diffusion of Si from Substrate into Au and AuPt Nanoalloy Nanorods.

Interdiffusion between Si substrate and nanorod arrays of Au, Pt, and AuPt nanoalloys is investigated at temperatures lower than the AuSi eutectic temperature. When the nanorod is pure Au, Si diffusion from the substrate is very rapid. Au atoms are completely replaced by Si, converting the nanostructure into one of Si nanorod arrays. Au is diffused out to the substrate. The Au nanorod arrays on Si are unstable. When the nanorod is pure Pt, however, no diffusion of Si into the nanorod or any silicide formation is observed. The Pt nanorods are stable on Si substrate. When the nanorods are an alloy of AuPt, interesting interactions occur. Si diffusion into the nanorods is rapid but the diffusing Si readily reacts with Pt forming PtSi while Au diffuses out to the substrate. After annealing, nanophases of Au, Pt, PtSi, and Si may be present within the nanorods. When the Pt content of the alloy is low (12 at%) all Pt atoms are converted to silicide and the extra Si atoms remain in elemental form, particularly near the tip of the nanorods. Hence, the presence of Au accelerates Si diffusion and the ensuing reaction to form PtSi, a phenomenon absents in pure Pt nanorods. When the Au content of the alloy is low, the Si diffusion would cease when all Au atoms have diffused out of the nanorod, thereby arresting the silicide formation resulting in excess Pt in elemental form within the nanorod. This is a technique of making Si nanorods with and without embedded PtSi nanophase consisting of heterojunctions which could have unique properties.

PTFEP-Al2O3 hybrid nanowires reducing thrombosis and biofouling.

Thrombosis and bacterial infection are major problems in cardiovascular implants. Here we demonstrated that a superhydrophobic surface composed of poly(bis(2,2,2-trifluoroethoxy)phosphazene) (PTFEP)-Al2O3 hybrid nanowires (NWs) is effective to reduce both platelet adhesion/activation and bacterial adherence/colonization. The proposed approach allows surface modification of cardiovascular implants which have 3D complex geometries.

Mapping the transition to superwetting state for nanotextured surfaces templated from block-copolymer self-assembly.

Adding roughness to hydrophilic surfaces is generally expected to enhance their wetting by water. Indeed, global free energy minimization predicts decreasing contact angles when roughness factor or surface energy increases. However, experimentally it is often found that water spreading on rough surfaces is impeded by pinning effects originating from local free energy minima; an effect, largely neglected in scientific literature. Here, we utilize Laplace pressure as a proxy for these local minima, and we map the transition to a superwetting state of hydrophilic nano-textured surfaces in terms of surface chemistry and texture geometry. We demonstrate the effect for polymer model surfaces templated from block-copolymer self-assembly comprising dense, nano-pillar arrays exhibiting strong pinning in their pristine state. By timed argon plasma exposure, we tune surface chemistry to map the transition into the superwetting state of low contact angle, which we show coincide with the surface supporting hemiwicking flow. For the near-ideal model surfaces, the transition to the superwetting state occurs below a critical material contact angle of ∼50°. We show that superwetting surfaces possess anti-fogging properties, and demonstrate long term stability of the superwetting effect by coating the nanotextured surfaces with ∼10 nm thin films of either tungsten or silica.

ITO with embedded silver grids as transparent conductive electrodes for large area organic solar cells.

In this work, development of semi-transparent electrodes for efficient large area organic solar cells (OSCs) has been demonstrated. Electron beam evaporated silver grids were embedded in commercially available ITO coatings on glass, through a standard negative photolithography process, in order to improve the conductivity of planar ITO substrates. The fabricated electrodes with embedded line and square patterned Ag grids reduced the sheet resistance of ITO by 25% and 40%, respectively, showing optical transmittance drops of less than 6% within the complete visible light spectrum for both patterns. Solution processed bulk heterojunction OSCs based on PTB7:[70]PCBM were fabricated on top of these electrodes with cell areas of 4.38 cm2, and the performance of these OSCs was compared to reference cells fabricated on pure ITO electrodes. The Fill Factor (FF) of the large-scale OSCs fabricated on ITO with embedded Ag grids was enhanced by 18% for the line grids pattern and 30% for the square grids pattern compared to that of the reference OSCs. The increase in the FF was directly correlated to the decrease in the series resistance of the OSCs. The maximum power conversion efficiency (PCE) of the OSCs was measured to be 4.34%, which is 23% higher than the PCE of the reference OSCs. As the presented method does not involve high temperature processing, it could be considered a general approach for development of large area organic electronics on solvent resistant, flexible substrates.

Highly Stable Monocrystalline Silver Clusters for Plasmonic Applications.

Plasmonic sensor configurations utilizing localized plasmon resonances in silver nanostructures typically suffer from the rapid degradation of silver under ambient atmospheric conditions. In this work, we report on the fabrication and detailed characterization of ensembles of monocrystalline silver nanoparticles (NPs), which exhibit a long-term stability of optical properties under ambient conditions without any protective treatments. Ensembles with different densities (surface coverages) of size-selected NPs (mean diameters of 12.5 and 24 nm) on quartz substrates are fabricated using the cluster-beam technique and characterized by linear spectroscopy, two-photon-excited photoluminescence, surface-enhanced Raman scattering microscopy, and transmission electron, helium ion, and atomic force microscopies. It is found that the fabricated ensembles of monocrystalline silver NPs preserve their plasmonic properties (monitored with optical spectroscopy) and strong field enhancements (revealed by surface-enhanced Raman spectroscopy) at least 5 times longer as compared to chemically synthesized silver NPs with similar sizes. The obtained results are of high practical relevance for the further development of sensors, resonators, and metamaterials utilizing the plasmonic properties of silver NPs.

Compact wavelength add-drop multiplexers using Bragg gratings in coupled dielectric-loaded plasmonic waveguides.

We report a novel design of a compact wavelength add-drop multiplexer utilizing dielectric-loaded surface plasmon-polariton waveguides (DLSPPWs). The DLSPPW-based configuration exploits routing properties of directional couplers and filtering abilities of Bragg gratings. We present practical realization of a 20-µm-long device operating at telecom wavelengths that can reroute optical signals separated by approximately 70 nm in the wavelength band. We characterize the performance of the fabricated structures using scanning near-field optical microscopy as well as leakage-radiation microscopy and support our findings with numerical simulations.

Surface plasmon polariton excitation by second harmonic generation in single organic nanofibers.

Coherent local excitation of surface plasmon polaritons (SPPs) by second-harmonic generation (SHG) in individual aligned crystalline organic functionalized para-phenylene nanofibers deposited on a thin silver film is demonstrated. The SH-SPP generation is considered theoretically and investigated experimentally with angular-resolved leakage radiation spectroscopy for normal incidence of the excitation beam. Both measurements and simulations show asymmetric excitation of left- and right-propagating SH-SPPs, which is explained as an effect of fiber molecules being oriented at an angle relative to the silver film surface.

Optical dipole mirror for cold atoms based on a metallic diffraction grating.

We report on the realization of a plasmonic dipole mirror for cold atoms based on a metallic grating coupler. A cloud of atoms is reflected by the repulsive potential generated by surface plasmon polaritons (SPPs) excited on a reflection gold grating by a 780 nm laser beam. Experimentally and numerically determined mirror efficiencies are close to 100%. The intensity of SPPs above a real grating coupler and the atomic trajectories, as well as the momentum dispersion of the atom cloud being reflected, are computed. A suggestion is given as to how the plasmonic mirror might serve as an optical atom chip.

The interplay between localized and propagating plasmonic excitations tracked in space and time.

In this work, the mutual coupling and coherent interaction of propagating and localized surface plasmons within a model-type plasmonic assembly is experimentally demonstrated, imaged, and analyzed. Using interferometric time-resolved photoemission electron microscopy the interplay between ultrashort surface plasmon polariton wave packets and plasmonic nanoantennas is monitored on subfemtosecond time scales. The data reveal real-time insights into dispersion and localization of electromagnetic fields as governed by the elementary modes determining the functionality of plasmonic operation units.

Measurement of surface plasmon autocorrelation functions.

In this paper we demonstrate the realization of an autocorrelator for the characterization of ultrashort surface plasmon polariton (SPP) pulses. A wedge shaped structure is used to continuously increase the time delay between two interfering SPPs. The autocorrelation signal is monitored by non-linear two-photon photoemission electron microscopy. The presented approach is applicable to other SPP sensitive detection schemes that provide only moderate spatial resolution and may therefore be of general interest in the field of ultrafast plasmonics.

Morphological tuning of the plasmon dispersion relation in dielectric-loaded nanofiber waveguides.

Understanding the impact of lateral mode confinement in plasmonic waveguides is of fundamental interest regarding potential applications in plasmonic devices. The knowledge of the frequency-wave vector dispersion relation provides the full information on electromagnetic field propagation in a waveguide. This Letter reports on the measurement of the real part of the surface plasmon polariton dispersion relation in the near infrared spectral regime for individual nanoscale plasmonic waveguides, which were formed by deposition of para-hexaphenylene (p-6P) based nanofibers on top of a gold film. A detailed structural characterization of the nanofibers provides accurate information on the dimensions of the investigated waveguides and enables us to quantify the effect of mode confinement by comparison with experimental results from continuous p-6P films and calculations based on the effective index method.

Surface plasmon polariton propagation in organic nanofiber based plasmonic waveguides.

Plasmonic wave packet propagation is monitored in dielectric-loaded surface plasmon polariton waveguides realized from para-hexaphenylene nanofibers deposited onto a 60 nm thick gold film. Using interferometric time resolved two-photon photoemission electron microscopy we are able to determine phase and group velocity of the surface plasmon polariton (SPP) waveguiding mode (0.967c and 0.85c at λ(Laser) = 812nm) as well as the effective propagation length (39 µm) along the fiber-gold interface. We furthermore observe that the propagation properties of the SPP waveguiding mode are governed by the cross section of the waveguide.

Mapping surface plasmon polariton propagation via counter-propagating light pulses.

In an interferometric time-resolved photoemission electron microscopy (ITR-PEEM) experiment, the near-field associated with surface plasmon polaritons (SPP) can be locally sensed via interference with ultrashort laser pulses. Here, we present ITR-PEEM data of SPP propagation at a gold vacuum interface recorded in a counter-propagating pump-probe geometry. In comparison to former work this approach provides a very intuitive real-time access to the SPP wave packet. The quantitative analysis of the PEEM data enables us to determine in a rather direct manner the propagation characteristics of the SPP.