Multiple Surface Plasmon Resonances in Compound Structure with Metallic Nanoparticle and Nanohole Arrays

The optical properties of a compound structure with metallic nanoparticle and nanohole arrays are numerically investigated by the means of finite-difference time domain method. We report on the observation of multi-valleys in the reflection spectra due to the excitation of surface plasmon (SP) resonant modes of the compound structure. Simulation results show that multiple SP resonances consist of surface plasmon polaritons on the gold film, localized surface plasmons on the nanoparticles, and coupling mode between them. These findings are important for applications utilizing multiple surface plasmon resonances.     

Plasmonic Coupling Effect in Ag Nanocap–Nanohole Pairs for Surface-Enhanced Raman Scattering

A plasmonic coupling structure composed of Ag nanocap–nanohole pairs was fabricated through a novel and facile method. Both surface-enhanced Raman scattering (SERS) measurements and numerical simulations show that the cap-hole system produces much larger electric field enhancement and SERS signal than the isolated structures, which is due to the plasmonic coupling effect between the gap of the cap and the hole. Additionally, the plasmonic enhancement is sensitive to the gap size, which can be controlled by the Ag layer thickness during the evaporation process. A maximum enhancement factor of 1.1×10⁸ can be obtained with optimized gap size.     

Large-Area Bowtie Nanoantenna Arrays Fabricated with Economic Oxygen Plasma-Assisted Nanosphere Lithography

Bowtie nanoantenna arrays were fabricated using plasma-assisted nanosphere lithography. The gap of each bowtie nanoantenna was precisely controlled by tuning the oxygen plasma treatment time, and gap distance as small as 30 nm was successfully fabricated. The occurrence of plasmon coupling and the functionality of the bowtie nanoantenna arrays were experimentally and theoretically verified. The plasma treatments help to change the size and gap distance of the nanoparticle arrays to match a specific surface plasmon resonance wavelength. The fabricated nanoantenna array covered a large area (∼1 cm²) and was suitable for large-scale fabrication with simple scale-up of the fabrication instruments, which should lead to novel new applications.     

Quantum Theory of Surface Plasmon Polaritons: Planar and Spherical Geometries

A quantum theory of retarded surface plasmons on a metal–vacuum interface is formulated, by analogy with the well-known and widely exploited theory of exciton-polaritons. The Hamiltonian for mutually interacting instantaneous surface plasmons and transverse electromagnetic modes is diagonalized with recourse to a Hopfield–Bogoljubov transformation, in order to obtain a new family of modes, to be identified with retarded plasmons. The interaction with nearby dipolar emitters is treated with a full quantum formalism based on a general definition of modal effective volumes. The illustrative cases of a planar surface and of a spherical nanoparticle are considered in detail. In the ideal situation of absence of dissipation, as an effect of the conservation of in-plane wavevector, retarded plasmons on a planar surface represent true stationary states (which are usually called surface plasmon polaritons), whereas retarded plasmons in a spherical nanoparticle, characterized by frequencies that overlap with the transverse electromagnetic continuum, become resonances with a finite radiative broadening. The theory presented constitutes a suitable full quantum framework for the study of nonperturbative and nonlinear effects in plasmonic nanosystems.     

Surface Plasmon Enhancement of Optical Absorption in Thin-Film Silicon Solar Cells

Strong electromagnetic field enhancement that occurs under conditions of the surface plasmon excitation in metallic nanoparticles deposited on a semiconductor surface is a very efficient and promising tool for increasing the optical absorption within semiconductor solar cells and, hence, their photocurrent response. The enhancement of the optical absorption in thin-film silicon solar cells via the excitation of localized surface plasmons in spherical silver nanoparticles is investigated. Using the effective medium model, the effect of the nanoparticle size and the surface coverage on that enhancement is analyzed. The optimum configuration and the nanoparticle parameters leading to the maximum enhancement in the optical absorption and the photocurrent response in a single p-n junction silicon cell are obtained. The effect of coupling between the silicon layer and the surface plasmon fields on the efficiency of the above enhancement is quantified as well.     

A Three-Dimensional Plasmonic Nanostructure with Extraordinary Optical Transmission

We report a 3D plasmonic nanostructure having an extraordinary optical transmission due to localized surface plasmon (LSP) coupling between nanoholes and nanodisks. The nanostructure contains a free-standing gold nanohole array (NHA) film above a cavity and an array of nanodisks at the bottom of the cavity that is aligned with the NHA. For the device, the LSP-mediated resonance position was dependent on the hole and nanodisk diameter as well as the separation distance. Also, the effect of LSP coupling between each hole and corresponding nanodisk became negligible for cavities deeper than 200 nm as observed as a disappearance of the LSP resonance. The greatest LSP resonance transmission and the highest electric field intensity were observed for the structure with the shallowest cavity. In addition, the structure had high surface plasmon resonance sensitivity and may have potential for surface-enhanced Raman spectroscopy and optical trapping applications.     

Single-Particle Spectroscopy of Supported Silver Clusters on Silicon: Substrate Effects on Localized Surface Plasmons

The presence of a surrounding medium strongly affects the spectral properties of localized surface plasmons at metallic nanoparticles. Vice versa, plasmonic resonances have large impact on the electric polarization in a surrounding or supporting material. For applications, e.g., in light-converting devices, the coupling of localized surface plasmons with polarizations in semiconducting substrates is of particular importance. Using photoemission electron microscopy with tunable laser excitation, we perform single-particle spectroscopy of silver nanoclusters directly grown on Si(100). Two distinct localized surface plasmon modes are observed as resonances in the two-photon photoemission signals from individual silver clusters. The strengths of these resonances strongly depend on the polarization of the exciting electric field, which allows us to assign them to plasmon modes with polarizations parallel and perpendicular, respectively, to the supporting silicon substrate. Our mode assignment is supported by simulations which provide insight into the mutual interaction of charge oscillations at the particle surface with electric polarizations at the silver/silicon interface.

     

Effect of secondary structure on single nucleotide polymorphism detection with a porous microarray matrix; implications for probe selection

Oligonucleotide arrays capable of detecting single nucleotide polymorphisms (SNPs) from amplified nucleic acid have many applications. The expected SNP is usually placed approximately in the center of the probe to ensure the maximum shift in Tm between complementary and SNP sequences. Unfortunately, different short probes (< 30 bases) selected using widely accepted criteria do not perform consistently in this type of assay. Here we present a systematic study on the effect of secondary structure on the ability of oligonucleotide probes to detect an SNP, using real-time array monitoring of a porous microarray substrate that incorporates a novel intra-array mixing system. These results demonstrate that, although positioning of an SNP in the middle of the probe is highly destabilizing, the effect of stable secondary structure on the signal obtained is so dramatic that such probes may be very insensitive. Therefore, if the SNP flanking sequence contains significant secondary structure, then more sensitive probes with good specificity may be obtained by positioning the mutation towards one end of the probe.     

Ring Gap Resonance Modes on Disk/Film Coupling System Caused by Strong Plasmon Interaction

Ring modes with large wave vectors cannot be easily excited on a single disk by the plane wave illumination with the polarization parallel to the disk interface. In this work, we show that special antisymmetric ring gap modes on the surface of the disk in close proximity to the metallic thin film can be excited in the visible light region of the electromagnetic spectrum. In the presence of the film, the strong plasmon interaction between disk and film causes ring gap modes to have lower energies and be more easily excited. We apply the plasmon hybridization method to illustrate the ring gap modes arising from the interaction between the localized disk plasmons and the continuum surface plasmons. The calculated hybridization data show good agreement with the results of finite element simulations. The excitation of ring gap modes provides further insight into the strong coupling of plasmons and the design of novel nanostructures.

     

Photoluminescence Quenching in Quantum Emitter,Metallic Nanoparticle,and Graphene Hybrids

We have developed a theory for photoluminescence quenching and plasmonic properties in hybrid nanosystems made from three nanosystems such as a quantum emitters, metallic nanoparticles, and graphene. The metallic nanoparticles and graphene have surface plasmons which couple with probe photons and create surface plasmon polaritons. Therefore, the excitons in the quantum emitters interact with surface plasmon polaritons via the dipole-dipole interaction. Due to this interaction, energy is exchanged between the nanosystems. The second quantized formulation and the quantum density matrix method have been used to calculate photoluminescence and the radiative and non-radiative decay processes in the presence of dipole-dipole interaction. We have compared our theory with experiments of two and three nanosystems, and a good agreement between theory and experiments is achieved. It has been found that the photoluminescence quenching in hybrid systems not only occurs through the direct non-radiative energy transfer from the quantum emitter to the metal nanoparticle and to graphene but also occurs through the indirect non-radiative energy transfer from quantum emitter to the metal nanoparticle via graphene and from the quantum emitter to graphene via metal nanoparticle. These are interesting findings and they can be used to fabricate nanoswitches and nanosensors for medical applications.     

Fluorescence Enhancement Caused by Plasmonics Coupling Between Silver Nano-Cubes and Silver Film

In this article, we experimentally investigated the plasmonics interaction in the system composed of Ag nano-cubes on Ag film with controlled distance. The distance is controlled by Rhodamine B (RhB)-doped polymethylmethacrylate (PMMA) film as the spacer, whose fluorescence intensity was then enhanced by the plasmonics interaction. Experimental results show that the fluorescence enhancement is sensitive to the thickness of the spacer. The largest enhancement factor obtained is 521 with the RhB-doped PMMA film of 10 nm thickness. For comparison, we also presented the fluorescence enhancement caused by only the localized surface plasmons from Ag nano-cubes on glass substrate coated with RhB-doped PMMA film, which gives out lower enhancement factors at the same thick spacer. Our experimental results are consistent with previous theoretical investigation and shows promising applications in fluorescence based bio-sensing or bio-imaging.     

Controllable Coupling of Localized and Propagating Surface Plasmons to Tamm Plasmons

We theoretically investigate the coupling between Tamm plasmons and localized surface plasmons (LSPs) as well as propagating surface plasmons (PSPs) in a multilayer structure consisting of a metallic nanowire array and a spatially separated metal–dielectric Bragg reflector (DBR). A clear anticrossing behavior of the resonances is observed in the dispersion diagram resulting from the coupling, which is well explained by the coupled oscillator model. The coupling also creates new hybrid LSP or PSP modes with narrow bandwidths and unique spectral features. Upon the excitation of these hybrid modes, the local fields underneath the nanowires for the hybrid LSPs or near the lower metal layer surface for the hybrid PSPs are both enhanced greatly as compared with those achieved in the structure without DBR, which has potential applications in nonlinear optics and surface-enhanced spectroscopies.     

AFM: a nanotool in membrane biology

Cellular membranes are vital for life. They confine cells and cytosolic compartments and are involved in virtually every cellular process. Cellular membranes form cellular contacts and focal adhesions, anchor the cytoskeleton, generate energy gradients, transform energy, transduce signals, move cells, and actively form compartments to assemble different membrane proteins into functional entities. But how do cellular membranes perform these tasks? What do the machineries of cellular membranes look like, and how are they controlled and guided? Atomic force microscopy (AFM) allows the observation of biological surfaces in their native environment at a signal-to-noise ratio superior to that of any optical microscopic technique. With a spatial resolution approaching approximately 1 nm, AFM can identify the supramolecular assemblies, characteristic structure, and functional conformation of native membrane proteins. In recent years, AFM has evolved from imaging applications to a multifunctional "laboratory on a tip" that allows observation and manipulation of the machineries of cellular membranes. In the force spectroscopy mode, AFM detects interactions between two single cells at molecular resolution. Force spectroscopy can also be used to probe the local elasticity, chemical groups, and receptor sites of live cells. Other applications locate molecular interactions driving membrane protein folding, assembly, and their switching between functional states. It is also possible to examine the energy landscape of biomolecular reactions, as well as reaction pathways, associated lifetimes, and free energy. In this review, we provide a flavor of the fascinating opportunities offered by the use of AFM as a nanobiotechnological tool in modern membrane biology.     

Sensitive label-free biosensors by using gap plasmons in gold nanoslits

The detection sensitivities of gap plasmons in gold nanoslit arrays are studied and compared with surface plasmons on outside surface. The nanoslit arrays were fabricated in a 130 nm-thick gold film with various slit widths. For transverse-magnetic (TM) incident wave, the 600 nm-period nanoslit array shows two distinguishable transmission peaks corresponding to the resonances of gap plasmons and surface plasmons, respectively. The surface sensitivities for both modes were compared by coating thin SiO(2) film and different biomolecules on the nanoslit arrays. Our experimental results verify gap plasmons are more sensitive than conventional surface plasmons. Its detection sensitivity increases with the decrease of slit width. The gap plasmon is one order of magnitude sensitive than the surface plasmon for slit widths smaller than 30 nm. We attribute this high sensitivity to the large overlap between biomolecules and nanometer-sized gap plasmons.     

Optical Absorption in Overcoats of Nanoparticle Arrays on a Metallic Substrate

Surface plasma oscillations in metallic particles as well as in thin metallic films have been studied extensively in the past decades. New features regarding surface plasma excitations are, however, constantly discovered, leading, for example, to surface-enhanced Raman scattering studies and enhanced optical transmission though metal films with nanohole arrays. In the present work, the role of a metallic substrate is examined in two cases, one involving an overcoat of dielectric nanoparticles and the other an overcoat of metallic nanoparticles. Theoretical results are obtained by modeling the nanoparticles as forming a two-dimensional, hexagonal lattice of spheres. The scattered electromagnetic field is then calculated using a variant of the Green function method. Comparison with experimental results is made for nanoparticles of tungsten oxide and tin oxide deposited on either gold or silver substrates, giving qualitative agreement on the extra absorption observed when the dielectric nanoparticles are added to the metallic surfaces. Such absorption would be attributed to the mirror image effects between the particles and the substrate. On the other hand, calculations of the optical properties of silver or gold nanoparticle arrays on a gold or a silver substrate demonstrate very interesting features in the spectral region from 400 to 1,000 nm. Interactions between the nanoparticle arrays surface plasmons and their images in the metallic substrate would be responsible for the red shift observed in the absorption resonance. Moreover, effects of particle size and ambient index of refraction are studied, showing a great potential for applications in biosensing with structures consisting of metallic nanoparticle arrays on metallic substrates.     

Plasmon-Enhanced Fluorescence Biosensors: a Review

Surfaces of metallic films and metallic nanoparticles can strongly confine electromagnetic field through its coupling to propagating or localized surface plasmons. This interaction is associated with large enhancement of the field intensity and local optical density of states which provides means to increase excitation rate, raise quantum yield, and control far field angular distribution of fluorescence light emitted by organic dyes and quantum dots. Such emitters are commonly used as labels in assays for detection of chemical and biological species. Their interaction with surface plasmons allows amplifying fluorescence signal (brightness) that accompanies molecular binding events by several orders of magnitude. In conjunction with interfacial architectures for the specific capture of target analyte on a metallic surface, plasmon-enhanced fluorescence (PEF) that is also referred to as metal-enhanced fluorescence (MEF) represents an attractive method for shortening detection times and increasing sensitivity of various fluorescence-based analytical technologies. This review provides an introduction to fundamentals of PEF, illustrates current developments in design of metallic nanostructures for efficient fluorescence signal amplification that utilizes propagating and localized surface plasmons, and summarizes current implementations to biosensors for detection of trace amounts of biomarkers, toxins, and pathogens that are relevant to medical diagnostics and food control.

     

Comparison of the direct electrochemistry of glucose oxidase immobilized on the surface of Au, CdS and ZnS nanostructures

A novel fluorescence biosensing strategy for simple, rapid and sensitive selecting quadruplex-binding ligands was reported by using graphene oxide (GO) as the fluorescence quencher. Data from transmission electron microscopy (TEM), atomic force microscopy (AFM) image, Fourier transform infrared (FT-IR) spectroscopy and Raman spectroscopy demonstrated that single-layered GO sheets were successfully prepared with well dispersion in aqueous solution. The fluorescein amidite (FAM)-labeled signal probe first adsorbed onto the surface of GO through π-stacking interaction between the ring structure in the nucleobases and the hexagonal cells of GO, and the fluorescence of the dye was quenched. When the quadruplex-binding ligands were introduced, the signal probe folded to form intramolecular G-quadruplex structure, which led to the releasing of FAM-labeled signal probe from the surface of GO and the fluorescence intensity recovered. Three series of Chinese medicine monomers were investigated by the proposed method, and the flavonoids were demonstrated to be the potential quadruplex-binding ligands by fluorescence measurement and melting temperature analysis. The results indicated that this strategy offers a simple, rapid and sensitive method for screening G-quadruplex ligands and it could find wide applications in the discovery of new antitumor drugs.     

The Focusing and Talbot Effect of Periodic Arrays of Metallic Nanoapertures in High-Index Medium

Three finite-sized two-dimensional (2D) periodic arrays of metallic nanoapertures with the shape of nanowave, nanohole, and nanodot have been developed. Using water as an output medium, although the operating wavelengths are larger than the array period, both the focusing and far-field plasmon Talbot effect are experimentally observed, showing a good agreement with the 2D finite-difference time-domain (FDTD) simulation results. The focusing performance in both cases, with the output medium of air and of water, is compared. A detailed investigation of the plasmon Talbot revivals reveals that they are composed of subwavelength hotspots with the size of ～0.5λ distributed in the same array period as the original device. Three-dimensional FDTD simulations prove that the existence of surface plasmons (SPs) exhibits an enhanced optical transmission at some SP resonant wavelengths dependent on the output medium. Additionally, it is demonstrated that the Talbot revivals provide a high-resolution mean to distinguish the slight geometric nonuniformity in periodic nanostructures.     

Discrimination of DNA hybridization using chemical force microscopy.

Atomic force microscopy (AFM) can be used to probe the mechanics of molecular recognition between surfaces. In the application known as "chemical force" microscopy (CFM), a chemically modified AFM tip probes a surface through chemical recognition. When modified with a biological ligand or receptor, the AFM tip can discriminate between its biological binding partner and other molecules on a heterogeneous substrate. The strength of the interaction between the modified tip and the substrate is governed by the molecular affinity. We have used CFM to probe the interactions between short segments of single-strand DNA (oligonucleotides). First, a latex microparticle was modified with the sequence 3'-CAGTTCTACGATGGCAAGTC and epoxied to a standard AFM cantilever. This DNA-modified probe was then used to scan substrates containing the complementary sequence 5'-GTCAAGATGCTACCGTTCAG. These substrates consisted of micron-scale, patterned arrays of one or more distinct oligonucleotides. A strong friction interaction was measured between the modified tip and both elements of surface-bound DNA. Complementary oligonucleotides exhibited a stronger friction than the noncomplementary sequences within the patterned array. The friction force correlated with the measured strength of adhesion (rupture force) for the tip- and array-bound oligonucleotides. This result is consistent with the formation of a greater number of hydrogen bonds for the complementary sequence, suggesting that the friction arises from a sequence-specific interaction (hybridization) of the tip and surface DNA.     

Atomic Force Microscopy and pharmacology: From microbiology to cancerology

Background

Atomic Force Microscopy (AFM) has been extensively used to study biological samples. Researchers take advantage of its ability to image living samples to increase our fundamental knowledge (biophysical properties/biochemical behavior) on living cell surface properties, at the nano-scale.

Scope of review

AFM, in the imaging modes, can probe cells morphological modifications induced by drugs. In the force spectroscopy mode, it is possible to follow the nanomechanical properties of a cell and to probe the mechanical modifications induced by drugs. AFM can be used to map single molecule distribution at the cell surface. We will focus on a collection of results aiming at evaluating the nano-scale effects of drugs, by AFM. Studies on yeast, bacteria and mammal cells will illustrate our discussion. Especially, we will show how AFM can help in getting a better understanding of drug mechanism of action.

Major conclusions

This review demonstrates that AFM is a versatile tool, useful in pharmacology. In microbiology, it has been used to study the drugs fighting Candida albicans or Pseudomonas aeruginosa. The major conclusions are a better understanding of the microbes' cell wall and of the drugs mechanism of action. In cancerology, AFM has been used to explore the effects of cytotoxic drugs or as an innovative diagnostic technology. AFM has provided original results on cultured cells, cells extracted from patient and directly on patient biopsies.

General significance

This review enhances the interest of AFM technologies for pharmacology. The applications reviewed range from microbiology to cancerology.