The interaction of biomolecules and solid-state nanomaterials at the nano-bio interfaces is a long-lasting research topic in nanotechnology. Historically, fundamental problems, such as the electron transfer, energy transfer, and plasmonic interaction at the bio-nano interfaces, have been intensively studied, and revolutionary technologies, such as molecular electronics, peptide chips, nanoplasmonic sensors, have been created. With the combined effort of molecular dynamics simulation and surface-enhanced Raman spectroscopy, we studied the external electric field-induced conformation changes of dodecapeptide probes tethered to a nanostructured metallic surface. Through this study, we demonstrated a reversible manipulation of the biomolecule conformations as well as an in situ eletro-optical detection of the subnanometer conformational changes at the bio-nano interfaces. Based on the proof-of-concept established in this study, we further propose a novel nanophotonic peptide phosphorylation sensor for high-sensitive peptide kinase profiling. We have also demonstrated the same SERS nano-bio-chip can be used for environmental monitoring applications, such as detection of contaminants in drinking water at ultralow concentrates. The fabrication of this nanosensor is based on a single step, lithography-less nanomanufacturing process, which can produce hundreds of these chips in several minutes with nearly 100% yield and uniformity. Therefore, the demonstrated research can be readily translated into industrial mass productions.

Cancer has become one of most significant death reasons and causes approximately 7.9 million human deaths worldwide each year. The challenge to detect cancer at an early stage makes cancer-related biomarkers sensing attract more and more research interest and efforts. Surface-enhanced Raman scattering (SERS) provides a promising method for various biomarkers (DNA, RNA, protein, et al.) detection due to its high sensitivity, specificity and capability for multiple analytes detection. Raman spectroscopy is a non-destructive photon-scattering technique, which provides molecule-specific information on molecular vibrational energy levels. SERS takes advantage of plasmonic effects and can enhance Raman signal up to 10¹⁵ at “hot spots”. Due to its excellent sensitivity, SERS has been capable of achieving single-molecule detection limit. Local pH environment has been identified to be a potential biomarker for cancer diagnosis since solid cancer contains highly acidic environments. A near-infrared (NIR) SERS nanoprobe based on gold nanostars for pH sensing is developed for future cancer detection. Near-infrared (NIR) light is more suitable for in vivo applications because of its low attenuation rate and tissue auto fluorescence. SERS spectrum of pH reporter under various pH environments is monitored and used for pH sensing. Furthermore, density functional theory (DFT) calculation is performed to investigate Raman spectra changes with pH at the molecular level. The study demonstrates that SERS is a sensitive tool to monitor minor molecular structural changes due to local pH environment for cancer detection.

The Wilms tumor gene (WT1) is a biomarker overexpressed in more than 90% of acute myeloid leukemia patients. Fast and sensitive detection of the WT1 in blood samples would allow monitoring of the minimal residual disease during clinical remission and would permit early detection of a potential relapse in acute myeloid leukemia. In this work, Surface Enhanced Raman Spectroscopy (SERS) based detection of the WT1 sequence using bifunctional, magnetic core – gold shell nanoparticles is presented. The classical co-precipitation method was applied to generate magnetic nanoparticles which were coated with a gold shell after modification with aminopropyltriethoxy silane and subsequent deposition of gold nanoparticle seeds. Simple hydroquinone based reduction procedure was applied for the shell growing in water based reaction mixture at room temperature. Thiolated ssDNA probes of the WT1 sequence were immobilized as capture oligonucleotides on the gold surface. Malachite green was applied both for testing the amplification performance of the core-shell colloidal SERS substrate and also as label dye of the target DNA sequence. The SERS enhancer efficacy of the core-shell nanomaterial was compared with the efficacy of classical spherical gold particles produced using the conventional citrate reduction method. The core-shell particles were found not only to provide an opportunity for facile separation in a heterogeneous reaction system but also to be superior regarding robustness as SERS enhancers.

Surface-enhanced Raman scattering (SERS) spectroscopy can be a useful tool in regard to disease diagnosis and prevention. Advantage of SERS over conventional Raman spectroscopy is its significantly increased signal (up to factor of 10₆-10⁸) which allows detection of trace amounts of substances in the sample. So far, this technique is successfully used for analysis of food, pieces of art and various biochemical/biomedical samples. In this work, we survey the possibility of applying SERS spectroscopy for detection of trace components in urinary deposits. Early discovery together with the identification of the exact chemical composition of urinary sediments could be crucial for taking appropriate preventive measures that inhibit kidney stone formation or growth processes. In this initial study, SERS spectra (excitation wavelength - 1064 nm) of main components of urinary deposits (calcium oxalate, uric acid, cystine, etc.) were recorded by using silver (Ag) colloid. Spectra of 10^-3-10^-5 M solutions were obtained. While no/small Raman signal was detected without the Ag colloid, characteristic peaks of the substances could be clearly separated in the SERS spectra. This suggests that even small amounts of the components could be detected and taken into account while determining the type of kidney stone forming in the urinary system. We found for the first time that trace amounts of components constituting urinary deposits could be detected by SERS spectroscopy. In the future study, the analysis of centrifuged urine samples will be carried out.

We developed a SERS biosensor based on gold fishnets fabricated by using e-beam lithography. This device is used for glycerophosphoinositol (GroPIns) molecule sensing. GroPIns is an abundant component of cell cytosol and high GroPIns levels have been reported in several tumour cells. We demonstrate that our SERS sensor is able to accurately and quantitatively determine the concentration of GroPIns. These results indicate that SERS may provide a novel platform technology to identify GroPIns profiles in disease pathogenesis.

A plasmonic metal film with a subwavelength hole array (a mesh) is used to capture an individual subwavelength particle, like a single yeast cell or airborne dust particle, and an imaging infrared (IR) microscope, records a scatterfree, IR absorption spectrum of the particle. Individual spectra of wavelength scale particles usually suffer from large scattering effects. This paper starts by demonstrating the plasmonic nature of the mesh in the infrared, proceeds to how this special form of light (surface plasmon polariton mediated transmission resonance) leads to scatter-free IR absorption spectra of individual, subwavelength particles, and ends with work on yeast cells and dust particles from our laboratory air and a household filter.

New opportunity to improve a sensetivity of a label-free biomolecule detection in sensing systems based on microcavity evanescent wave optical sensors has been recently found and is being under intensive development. Novel technique based on combination of optical resonance on microring structures with plasmon resonance. Recently developed tools based on neural network data processing can realize real-time identification of biological agents. So combining advantages of plasmon enhancing optical microcavity resonance with identification tools can give a new platform for ulta sensitive label-free biomedical sensor. Our developed technique used standard glass and polymer microspheres as sensetive elements. They are fixed in the solution flow by adhesive layer on the surface being in the field of evanescence wave. Sensitive layer have been treated by gold nanoparticel (GN) solution. Another technique used thin film gold layers deposited on the substrate below adhesive. The light from a tuneable diode laser is coupled into the microsphere through a prism and was sharply focussed on the single microsphere. Images were recorded by CMOS camera. Normalized by free spectral range resonance shift of whispering gallery mode (WGM) and a relative efficiency of their excitation were used as input data for biomolecule classification. Both biomolecules and NP injection was obtained caused WGM spectra modification. But after NP treatment spectral shift and intensity of WGM resonances in biomolecule solutions increased. WGM resonances in microspheres fixed on substrate with gold layer with optimized layer thickness in biomolecule solutions also had higher intensity and spectra modification then without gold layer.

We present a three dimensional (3D) metallic nanostructure, which has transmission resonance properties related to both localized surface plasmons and propagating surface plasmon polaritons. Various geometrical dimensions of the 3D metallic nanostructures were studied by means of simulation and experiment with respect to resonance position, resonance line width and bulk sensitivity. Narrower resonance line width and higher bulk sensitivity were achieved for the 3D nanostructure compared to conventional nanohole arrays. Finally, a 3D metallic nanostructure functionalized with a biotinylated thiol could detect streptavidin, suggesting the device may have potential as a bio-sensor.

Surface Plasmon Resonance (SPR) is the base for some of the most sensitive label free optical fiber biosensors. However, most solutions presented to date require the use of fragile fiber optic structure such as adiabatic tapers or side polished fibers. On the other hand, long-period fiber gratings (LPG) present themselves as an interesting solution to attain an evanescent wave refractive index sensor platform while preserving the optical fiber integrity. The combination of these two approaches constitute a powerful platform that can potentially reach the highest sensitivities as it was recently demonstrated by detailed theoretical study [1, 2]. In this work, a LPG-SPR platform is explored in different configurations (metal coating between two LPG – symmetric and asymmetric) operating in the telecom band (around 1550 nm). For this purpose LPGs with period of 396 μm are combined with tailor made metallic thin films. In particular, the sensing regions were coated with 2 nm of chromium to improve the adhesion to the fiber and 16 nm of gold followed by a 100 nm thick layer of TiO2 dielectric material strategically chosen to attain plasmon resonance in the desired wavelength range. The obtained refractometric platforms were then validated as a biosensor. For this purpose the detection of thrombin using an aptamer based probe was used as a model system for protein detection. The surface of the sensing fibers were cleaned with isopropanol and dried with N2 and then the aminated thrombin aptamer (5’-[NH2]- GGTTGGTGTGGTTGG-3’) was immobilized by physisorption using Poly-L-Lysine (PLL) as cationic polymer. Preliminary results indicate the viability of the LPFG-SPR-APTAMER as a flexible platforms point of care diagnostic biosensors.

We present passive mode locking of a vertical external-cavity surface-emitting laser (VECSEL) in the red spectral range. The gain structure includes 20 compressively strained GaInP quantum wells (QWs), which are arranged in a resonant periodic gain design containing five packages of four quantum wells each. We use tensile strained AlGaInP barriers and cladding layers to compensate the strain introduced by the quantum wells. The semiconductor saturable absorber mirror (SESAM) includes two of the same quantum wells as used in the gain structure, positioned close to the surface. The semiconductor structure is grown by MOVPE in a near-resonant design and coated with a fused silica layer for an overall anti-resonant design. For tight focussing of the laser mode onto the absorber, we use a v-shaped cavity with an overall length of 179mm. Autocorrelation measurements show a FWHM pulse duration below 250 fs with side pulses arising due to the diamond heatspreader bonded onto the gain chip. The laser spectrum consists of a soliton-like part at 664.5 nm and a “continuum” which is also found in autocorrelation measurements perfomed in a Hanbury-Brown and Twiss type setup. An FFT based frequency analysis of the emitted pulse train shows a repetition rate of 836MHz. The SESAM charge carrier dynamics were investigated by pump-probe measurements. We observe a tri-exponential decay with a dominant fast decay time in the range of the pulse duration.

In this report we discuss the influence of plasmon excitations in a silver island film on the fluorescence of photosynthetic complex, peridinin-chlorophyll-protein (PCP). Control of the separation between these two components is obtained by fabricating a wedge layer of silica across the substrate, with a thickness from 0 to 46 nm. Continuous variation of the silica thickness allows for gradual change of interaction strength between plasmon excitations in the metallic film and the excited states of pigments comprising photosynthetic complexes. While the largest separation between the silver film and photosynthetic complexes results in fluorescence featuring a mono-exponential decay and relatively narrow distribution of intensities, the PCP complexes placed on thinner silica spacers show biexponential fluorescence decay and significantly broader distribution of total fluorescence intensities. This broad distribution is a signature of stronger sensitivity of fluorescence enhancement upon actual parameters of a hybrid nanostructure. By gradual change of the silica spacer thickness we are able to reproduce classical distance dependence of fluorescence intensity in plasmonic hybrid nanostructures on ensemble level. Experiments carried out for different excitation wavelengths indicate that the interaction is stronger for excitations resonant with plasmon absorption in the metallic layer.

Metal Enhanced Fluorescence (MEF) takes advantage of the coupling between surface plasmons, in either a metallic thin film or metallic nanoparticles, and fluorophores located in proximity of the metal, yielding an increase of the fluorophore emission. While MEF has been widely studied on metallic nanoparticles with the emphasis on creating brighter fluorescent labels, planar surfaces have not benefitted from the same attention. Here we investigate the influence of the surface roughness of a thin metallic film on the fluorescence enhancement. 50nm thick silver films were deposited on glass slides using either thermal evaporation with different evaporation currents or an electroless plating method based on the Tollens reaction to vary the surface roughness. Multiple layers of positively and negatively charged polyelectrolytes were deposited on top of the metallic coating to map out the enhancement factor as function of the gap between the metallic coating and fluorophore molecules covalently bound to the last polyelectrolyte layer. We show that fluorescence is enhanced by the presence of the metallic film, and in particular that the enhancement increases by a factor 3 to 40 for roughness ranging from 3 nm to 8 nm. Although these enhancement factors are modest compared to the enhancement produced by complex metallic nanoparticles or nano-patterned metallic thin films, the thin films used here are capable of supporting a plasmonic wave and offer the possibility of combining different techniques, such as surface plasmon resonance (with its higher refractive index sensitivity compared to localized plasmons) and MEF within a single device.

Metal Enhanced Fluorescence (MEF), a phenomenon arising when a fluorophore is in closed proximity to a metallic structure such as metallic films or nanostructures, is seen as a way to increase the amount of reactive oxygen species produced by the irradiation of the protoporphyrin IX (PpIX), a photosensitizer commonly used in photodynamic therapy. Here, we show a study of the distance-dependent of MEF by applying multiple layers of polyelectrolyte (PE) on silver nanoparticles (AgNPs) to progressively increase the distance between AgNPs and PpIX, covalently bond to the last polyelectrolyte layer as well as exploring the use of AgNPs of different sizes ranging from 40 to 100 nm. Up to four fold increase of PpIX fluorescence was observed when this photosensitizing agent is bounded onto 100 nm sized Ag NPs. The effective corresponding distance between AgNPs and PpIX is three layers of PE.

The wavelength and size dependencies of nonlinear scattering by a single gold nanosphere immersed in oil are presented. We show that the wavelength dependency fits well with the scattering spectrum by Mie solution, reflecting that the nonlinear scattering is dominated by the field enhancement from plasmonic effects. The tendency for different sizes is consistent with the results of degenerate four-wave mixing in the literature, showing that the saturation behavior is governed by the Kerr nonlinearity resonantly enhanced via intraband transition. Thus we conclude that the saturable scattering in our case is attributed to intraband χ(³⁾, with nonlinear behavior enhanced by LSPR.

The scattering of surface plasmon polariton (SPP) waves can be manipulated by various plasmonic structures. The plasmonic structure composed of arranged subwavelength nanobumps on a gold thin film is the promising structure to manipulation SPP wave. By controlling the geometric shape of the structures, the height, position, and pattern of scattered light from SPP wave can be modulated as desired. A clear single focusing spot can be reconstructed at a specific altitude by a particular curved structure with appropriate curvature and adjacent interspacing of nanobumps. The designed light patterns reconstructed by the focusing spot from the arranged curved structures at a specific observation plane are clearly demonstrated.

Recently there have been tremendous interests about the fabrication of the solid state nanopore due to its capability of the nanosize biosensor. In this report, the dynamics of the Au nanopore formation on the pyramidal membrane will be reported. The nanopores on the microfabricated Au coated SiO2 pyramid were fabricated using focused ion beam (FIB) and high energy electron beam techniques such as transmission electron microscopy (TEM), and field emission scanning electron microscopy (FESEM). For high scanning electron beam irradiation using FESEM, shrinking of the Au nanopore was always observed. The nanopore formation dependent upon the primary electron voltage, and the scan rate of the FESEM electron beam was carefully examined. The higher closing rates for the faster scan rate and the lower electron accelerating voltage are observed. For the TEM electron beam exposure, the closing or the opening of the pore was observed depending upon the electron beam current. We do believe that this phenomenon can be attributed to the capillary force and the vaporization of the materials on the viscous liquid membrane due to TEM electron beam irradiation.