Enhanced intrinsic fluorescence from carboxidized nano-sculptured thin films of silver and their application for label free dual detection of glycated hemoglobin.

Enhanced intrinsic fluorescence (~x103) from novel carboxidized nanosculptured thin films (CO-nSTFs) of silver is reported. The sources of intrinsic fluorescence, confirmed by X-ray photoelectron spectroscopy, are Ag2O grains and residual carbon formed on the outer layer of silver nSTFs when exposed to air, while the localized surface plasmons on silver nSTFs enhance this intrinsic fluorescence. The CO-nSTFs are optimized with respect to porosity for the maximum enhancement. A sensor developed by using the self-assembled monolayer technique on optimized CO-nSTF is used for the label free detection of glycated hemoglobin, performed by simultaneously using fluorescence imaging and spectroscopy. The specificity of the sensor is established from control experiments on hemoglobin. These novel nanorod like intrinsically fluorescent CO-nSTFs pose huge potential in label free biosensing, light sources, imaging and many more applications.

Highly sensitive and specific detection of E. coli by a SERS nanobiosensor chip utilizing metallic nanosculptured thin films.

A nanobiosensor chip, utilizing surface enhanced Raman spectroscopy (SERS) on nanosculptured thin films (nSTFs) of silver, was shown to detect Escherichia coli (E. coli) bacteria down to the concentration level of a single bacterium. The sensor utilizes highly enhanced plasmonic nSTFs of silver on a silicon platform for the enhancement of Raman bands as checked with adsorbed 4-aminothiophenol molecules. T-4 bacteriophages were immobilized on the aforementioned surface of the chip for the specific capture of target E. coli bacteria. To demonstrate that no significant non-specific immobilization of other bacteria occurs, three different, additional bacterial strains, Chromobacterium violaceum, Paracoccus denitrificans and Pseudomonas aeruginosa were used. Furthermore, experiments performed on an additional strain of E. coli to address the specificity and reusability of the sensor showed that the sensor operates for different strains of E. coli and is reusable. Time resolved phase contrast microscopy of the E. coli-T4 bacteriophage chip was performed to study its interaction with bacteria over time. Results showed that the present sensor performs a fast, accurate and stable detection of E. coli with ultra-small concentrations of bacteria down to the level of a single bacterium in 10 µl volume of the sample.

SERS biosensor using metallic nano-sculptured thin films for the detection of endocrine disrupting compound biomarker vitellogenin.

A biosensor chip is developed for the detection of a protein biomarker of endocrine disrupting compounds, vitellogenin (Vg) in aquatic environment. The sensor chip is fabricated by immobilizing anti-Vg antibody on 4-Aminothiophenol (4-ATP) coated nanosculptured thin films (nSTFs) of silver on Si substrates. The biosensor is based on the SERS of 4-ATP, enhanced by the Ag nSTFs. Before the fabrication of the sensor, the performance of the enhancement is optimized with respect to the porosity of nSTFs. Further, the biosensor is developed on the nSTF with optimized enhancement. The SERS signals are recorded from the sensor chip for varying concentrations of Vg. A control experiment is performed on another similar protein Fetuin to confirm the specificity of the sensor. The repeatability and reusability of the sensor, along with its shelf life are also checked. The limit of detection of the sensor is found to be 5 pg mL −1 of Vg in PBS within our experimental window. Apart from high sensitivity, specificity and reusability, the present sensor provides additional advantages of miniaturization, requirement of very small volumes of the analyte solution (15 µL) and fast response as compared to conventional techniques e.g., ELISA, as its response time is less than 3 minutes.

Giant Extra-Ordinary Near Infrared Transmission from Seemingly Opaque Plasmonic Metasurface: Sensing Applications.

In the present study, we report giant extra-ordinary transmission of near infrared (NIR) light, more than 90%, through a seemingly opaque plasmonic metasurface, which consists of two metal nano-slits arrays (MNSAs) with alternate opening arrangements. By using perfect coupling of the plasmonic modes formed between the sharp edges of the upper and lower MNSAs of silver, a giant, wavelength selective transmission could be obtained. The study is accompanied by optimization of electromagnetic (EM) field coupling for different interlayer spacings and lateral overlap between the two MNSAs to understand their significance in light transmission through the metasurface. The interlayer spacing between the MNSAs works as the transmitting channel for light. The optimization of performance with different fill factors and plasmonic metals was performed as well. Because of the excitation of extended surface plasmons (ESPs) generated at both the MNSAs, the metasurface can be used for refractive index (RI) sensing as one of its applications by using a transparent and flexible polymer, such as polydimethylsiloxane (PDMS), as substrate. The maximum sensitivity which could be achieved for the optimal configuration of the metasurface was 1435.71 nm/RIU, with a figure of merit (FOM) of 80 RIU-1 for 90.45% optical transmission of light for the refractive index variation of analyte medium from 1.33 to 1.38 RIU. The present study strengthens the concept of light funneling through subwavelength structures due to plasmons, which are responsible for light transmission through this seemingly opaque metasurface and finds use in highly sensitive, flexible, and cost-effective EOT-based sensors.

Simulation of a localized surface-plasmon-resonance-based fiber optic temperature sensor.

A fiber optic temperature sensor based on localized surface plasmon resonance of spherical gold nanoparticles embedded in a dielectric layer around the unclad core of a small portion of the fiber has been analyzed. Simulations have been carried out for a number of dielectric materials that show considerable changes in their refractive indices due to a change in the temperature in addition to having refractive indices higher than that of the fiber core. The analysis is based on the spectral interrogation method. The surface plasmons in metal nanoparticles have been excited by the light refracted through the core and the dielectric interface. The sensitivity of the sensor has been determined for each dielectric material used, and it is found to be the maximum for CdGeP(2) as a sensing medium. The temperature sensing range of the present sensor is also wide because the melting points of the metal and the fiber core, as well as the sensing medium, are large. The proposed fiber optic temperature sensor is compact, light weight, and highly sensitive with a wide temperature sensing range.

Theoretical modeling of a localized surface plasmon resonance based intensity modulated fiber optic refractive index sensor.

A localized surface plasmon resonance based fiber optic sensor for refractive index sensing has been analyzed theoretically. The effects of size of the spherical metal nanoparticle as well as the light sources on the performance of the sensor have been studied rigorously. It is observed that a diffuse light source along with an intensity modulation method gives better performance in terms of sensing range. In addition, the use of a diffuse source makes the sensing device very cheap and compact, which is an important issue for the commercial applications. The refractive index range of the sensor is larger than the ranges reported for various types of fiber optic sensors utilizing intensity modulation.

DNA origami nanorobot fiber optic genosensor to TMV.

In the quest of greater sensitivity and specificity of diagnostic systems, one continually searches for alternative DNA hybridization methods, enabling greater versatility and where possible field-enabled detection of target analytes. We present, herein, a hybrid molecular self-assembled scaffolded DNA origami entity, intimately immobilized via capture probes linked to aminopropyltriethoxysilane, onto a glass optical fiber end-face transducer, thus producing a novel biosensor. Immobilized DNA nanorobots with a switchable flap can then be actuated by a specific target DNA present in a sample, by exposing a hemin/G-quadruplex DNAzyme, which then catalyzes the generation of chemiluminescence, once the specific fiber probes are immersed in a luminol-based solution. Integrating organic nanorobots to inorganic fiber optics creates a hybrid system that we demonstrate as a proof-of-principle can be utilized in specific DNA sequence detection. This system has potential applications in a wide range of fields, including point-of-care diagnostics or cellular in vivo biosensing when using ultrathin fiber optic probes for research purposes.

Quantitative assessment of paraoxon adsorption to amphiphilic ß-sheet peptides presenting the catalytic triad of esterases.

Organophosphate compounds that are used as pesticides affect the nervous system by binding irreversibly to the active site of the enzyme acetylcholine esterase (AChE) and disrupting neuro-signaling nerve cells. In this study we characterized adsorption of paraoxon to a set of designed peptides that present different arrangements of the three amino acids of the AChE catalytic site: histidine, glutamic-acid and serine. The peptides set included two ß-strands with no net charge and three ß-hairpins that differ in their net charge. Circular dichroism, Thioflavin T assays and TEM images provided only qualitative insights on paraoxon binding to the different peptides. Paraoxon binding to the different peptides was measured with dialysis membrane tubes filled with the peptide solutions and suspended in a reservoir of paraoxon solution. Among all the tested peptides, the single strand peptide, denoted ssESH exhibited at 100 µM in random conformation prefibrillar state, the maximum paraoxon adsorption, with a binding mol ratio of one paraoxon per two peptides and an estimated equilibrium binding constant 5 ∗ 104 M-1. The three ß-hairpin peptides demonstrated that a net negative charge is unfavorable for paraoxon adsorption. Surface enhanced Raman spectroscopy measurements with ssESH enabled the detection of nanomolar adsorbed concentrations of paraoxon.

Engineering the hot spots in squared arrays of gold nanoparticles on a silver film.

Density of nanoparticle (NP) arrays affects the hot spots distribution and strength in NP-metal film (NP-MF) geometry. In-depth understanding of the variation of electromagnetic (EM) field enhancement with NPs density is essential for wide applications of the NP-MF geometry such as surface-enhanced spectroscopies and enhanced efficiency of optoelectronic devices. Here, we show that the field distribution in the NP array on the metal film is greatly enhanced and confined at the NP-NP junctions for very small horizontal gap (g) between neighboring NPs, whereas the fields at the NP-MF junction are extremely small. When gradually increasing g, the field enhancement at the NP-NP junction decreases, along with the gradually enhanced fields at the NP-MF junction. We show that there is an optimal value of horizontal gap (∼75 nm for 80 nm Au NP array on Ag film with 532 nm normal incidence), indicating that the average field enhancement in NP-MF geometry can be optimized by adjusting the horizontal gap. More importantly, it is found that the EM field enhancement is greatly decreased when g fulfills the requirement to couple the 532 nm incident light into SPPs, because of the interference between the LSPR and the SPPs, which leads to a Fano dip at the incident wavelength of 532 nm.