Ultrafast Nanodrum-on-Chip Pixels.

Environmentally friendly, ultrafast display pixels of micrometer sizes are fabricated with nanometer-thick gold films and Si/SiO2 wafers. The color displayed is due to both the plasmon response of the gold film and the optical interference from the Fabry-Peerot cavity formed by the underlying silicon substrate, the semitransparent gold film and the air gap between them. When an electric potential is applied to the gold film, the electrostatic force induces an attraction between the gold film and the silicon wafer. Due to the flexibility of the film, the size of the air gap changes, resulting in a changing color. By applying different driving signals, we have achieved cyan, magenta, and yellow reflected colors. The maximum switching rate of the pixel is primarily determined by the thickness dependence of the metal drum and its Young's modulus and is typically in the MHz regime.

SERS Endoscopy for Monitoring Intracellular Drug Dynamics.

Understanding the dynamics and distribution of medicinal drugs in living cells is essential for the design and discovery of treatments. The tools available for revealing this information are, however, extremely limited. Here, we report the application of surface-enhanced Raman scattering (SERS) endoscopy, using plasmonic nanowires as SERS probes, to monitor the intracellular fate and dynamics of a common chemo-drug, doxorubicin, in A549 cancer cells. The unique spatio-temporal resolution of this technique reveals unprecedented information on the mode of action of doxorubicin: its localization in the nucleus, its complexation with medium components, and its intercalation with DNA as a function of time. Notably, we were able to discriminate these factors for the direct administration of doxorubicin or the use of a doxorubicin delivery system. The results reported here show that SERS endoscopy may have an important future role in medicinal chemistry for studying the dynamics and mechanism of action of drugs in cells.

Andrographolide stabilized-silver nanoparticles overcome ceftazidime-resistant Burkholderia pseudomallei: study of antimicrobial activity and mode of action.

Burkholderia pseudomallei (B. pseudomallei) is a Gram-negative pathogen that causes melioidosis, a deadly but neglected tropical disease. B. pseudomallei is intrinsically resistant to a growing list of antibiotics, and alternative antimicrobial agents are being sought with urgency. In this study, we synthesize andrographolide-stabilized silver nanoparticles (andro-AgNPs, spherically shaped with 16 nm average diameter) that show excellent antimicrobial activity against B. pseudomallei, including ceftazidime-resistant strains, being 1-3 orders of magnitude more effective than ceftazidime and 1-2 orders of magnitude more effective than other green-synthesized AgNPs. The andro-AgNPs are meanwhile non-toxic to mammalian cell lines. The mode of action of Andro-AgNPs toward B. pseudomallei is unraveled by killing kinetics, membrane neutralization, silver ions (Ag+) release, reactive oxygen species (ROS) induction, membrane integrity, and cell morphology change studies. The antimicrobial activity and mode of action of andro-AgNPs against B. pseudomallei reported here may pave the way to alternative treatments for melioidosis.

Frequency Shift Surface-Enhanced Raman Spectroscopy Sensing: An Ultrasensitive Multiplex Assay for Biomarkers in Human Health.

The sensitive and selective detection of biomarkers for human health remains one of the grand challenges of the analytical sciences. Compared to established methods (colorimetric, (chemi) luminescent), surface-enhanced Raman spectroscopy (SERS) is an emerging alternative with enormous potential for ultrasensitive biological detection. Indeed even attomolar (10-18 M) detection limits are possible for SERS due to an orders-of-magnitude boosting of Raman signals at the surface of metallic nanostructures by surface plasmons. However, challenges remain for SERS assays of large biomolecules, as the largest enhancements require the biomarker to enter a "hot spot" nanogap between metal nanostructures. The frequency-shift SERS method has gained popularity in recent years as an alternative assay that overcomes this drawback. It measures frequency shifts in intense SERS peaks of a Raman reporter during binding events on biomolecules (protein coupling, DNA hybridization, etc.) driven by mechanical transduction, charge transfer, or local electric field effects. As such, it retains the excellent multiplexing capability of SERS, with multiple analytes being identifiable by a spectral fingerprint in a single read-out. Meanwhile, like refractive index surface plasmon resonance methods, frequency-shift SERS measures the shift of an intense signal rather than resolving a peak above noise, easing spectroscopic resolution requirements. SERS frequency-shift assays have proved particularly suitable for sensing large, highly charged biomolecules that alter hydrogen-bonding networks upon specific binding. Herein we discuss the frequency-shift SERS method and promising applications in (multiplex) biomarker sensing as well as extensions to ion and gas sensing and much more.

Materials design of vertically coupled plasmonic arrays.

Plasmonic metasurfaces have important applications in life science, optics, and catalysis. However, their industrial usage is limited by the challenges of high throughput nanofabrication. A promising solution is the transfer of a pattern into a substrate using block copolymers, nanostructured stamps or molds to create binary, three dimensional templates, which can then be decorated with plasmonically active metals. Here, we report on the optical properties of quasi-Babinet complementary arrays in the non-retarded regime investigated by finite-difference time-domain simulations. The structures consist of a nanopillar support, which is covered with metal disks on top of the pillars and a quasi-Babinet complementary hole array film at the base of the pillars. Strong vertical plasmonic coupling occurs for small separation distances of the plasmonic slabs. We present a comprehensive study of the near and far-field properties of such vertically coupled plasmonic arrays varying their critical geometric dimension and the employed metals with their intrinsic plasmonic material properties. In particular, we consider gold, silver, copper, aluminum, nickel, and palladium. Furthermore, the effect of the refractive index n of the nanopillar support between the range of n = 1.4 to n = 3.4 is investigated. The plasmonic slabs show tunable extraordinary transmission and large electric near-field enhancements, which are strongly dependent on the employed material and geometry. Further, we show that the templates are suitable for plasmonic heterostructures commonly used in plasmon-enhanced photocatalysis.

Excitation wavelength dependent surface enhanced Raman scattering of 4-aminothiophenol on gold nanorings.

Detailed understanding of the underlying mechanisms of surface enhanced Raman scattering (SERS) remains challenging for different experimental conditions. We report on an excitation wavelength dependent SERS of 4-aminothiophenol molecules on gold nanorings. SERS and normal Raman spectra, combined with well-characterized surface morphology, optical spectroscopy and electromagnetic (EM) field simulations of gold nanoring substrates indicate that the EM enhancement occurs at all three excitation wavelengths (532, 633 and 785 nm) employed but at short wavelengths (532 and 633 nm) charge transfer (CT) results in additional strong enhancements of particular Raman transitions. These results pave the way to further understanding the origin of the SERS mechanism.

Focusing plasmons in nanoslits for surface-enhanced Raman scattering.

The focusing of plasmons to obtain a strong and localized electromagnetic-field enhancement for surface-enhanced Raman scattering (SERS) is increasing the interest in using plasmonic devices as molecular sensors. In this Full Paper, we report the successful fabrication and demonstration of a solid-state plasmonic nanoslit-cavity device equipped with nanoantennas on a freestanding thin silicon membrane as a substrate for SERS. Numerical calculations predict a strong and spatially localized enhancement of the optical field in the nanoslit (6 nm in width) upon irradiation. The predicted enhancement factor of SERS was 5.3 x 10(5), localized in an area of just 6 x 1.5 nm(2). Raman spectroscopy and imaging confirm an enhancement factor of approximately 10(6) for SERS from molecules chemisorbed at the nanoslit, and demonstrate the electromagnetic-field-enhancing function of the plasmonic nanoantennas. The freestanding membrane is open on both sides of the nanoslit, offering the potential for through-slit molecular translocation studies, and opening bright new perspectives for SERS applications in real-time (bio)chemical analysis.