Tailored Aggregate-Free Au Nanoparticle Decorations with Sharp Plasmonic Peaks on a U-Type Optical Fiber Sensor by Nanosecond Laser Irradiation

A novel experimental methodology is presented for fabricating U-shaped optical fiber probes decorated with aggregate-free Au nanoparticles exhibiting sharp localized surface plasmon resonance (LSPR) spectra. The U-type tip is coated with gold nanoparticles (AuNPs) using a simple and time-efficient dip-coating procedure, without initially taking any care to prevent the formation of nanoparticle aggregates in the coated area. In a second step, the coating was irradiated with a few tens of laser pulses of 5-ns duration at 532 nm with intensities in the range of 2–14 MW/cm², leading to the formation of aggregate-free LSPR optical fiber probes. The process was monitored and controlled in real time through the changes induced into the fiber’s extinction spectra by the laser irradiation, and the coated fibers were characterized by electron microscopy. The proposed methodology resulted into the fabrication of U-type optical fiber probes coated with AuNPs exhibiting a sharp plasmon peak, which is a perquisite for their application as sensing devices.     

Analysis of recombinant protein expression using localized surface plasmon resonance (LSPR)

The localized surface plasmon resonance (LSPR)-based optical biosensor using nano-structures of noble metals has been considered as a useful tool for label-free detection of DNA hybridization and protein-protein interactions. We fabricated LSPR-based optical biosensors using gold nano-islands (nominal thickness; 75 A) on glass substrates that were easily made using the conventional fabrication methods. The formation of gold nano-islands on glass substrates was realized by heat treatment of thin gold film deposited with a low deposition rate (approximately 0.05 A/s). The morphologies of sensor surfaces composed of gold nano-islands were observed using an atomic force microscope (AFM) with a non-contact mode. To investigate the sensing capacity of the gold nano-island sensor for the binding of proteins by affinity interactions, the streptavidin and biotin interaction was used as a model system. In addition, detection of recombinant glutathione-S-transferase (GST)-tagged human interleukin-6 (hIL6) expressed in Escherichia coli was carried out by LSPR. It is expected that the LSPR sensors composed of gold nano-islands can be an alternative to traditional methods such as SDS-polyacrylamide gel electrophoresis (SDS-PAGE) for fast analysis of protein expression.     

Dielectric Nanocup Coating Effect on the Resonant Optical Properties of Individual Au Nanosphere

By finite element method (FEM), dielectric nanocup coating effect on the resonant optical properties of individual Au nanosphere was investigated. It is demonstrated not deleterious to the sensing signals of the nanosphere. The proposed nanocomposite provides an interesting localized surface plasmon resonance (LSPR) sensor with quadratic response, which refractive index (RI) sensitivity is revealed to increase with the RI both of its surrounding and local environment. The differences between the LSPR peak positions of the nanocomposite measured from far-field and near-field spectra are discussed, too. It is believed to shed light on the future applications in surface enhanced Raman spectroscopy, biochemical sensing, and detections.     

Highly Stable Plasmonic Nanostructures on a Nickel-Sputtered Glass and Polymeric Optical Fiber Sensors

Plasmonics - This study shows development of highly sensitive and stable localized surface plasmon resonance (LSPR)-active U-bent glass and polymeric optical fiber (GOF and POF) sensor probes by a...     

Engineering the Optical Response of the Novel Plasmonic Binary Nanohole Array

The phenomenon of extraordinary optical transmission (EOT) due to its advantages has been considered by researchers in various applications, and in recent years, many efforts have been made to engineer these structures to get the best possible response for desired applications. In this work, the optical properties of novel binary gold nanohole arrays are investigated theoretically. We engineered the optical response of the system by adjusting the ratio of contribution of surface plasmon polariton (SPP) to localized surface plasmon resonance (LSPR) through the manipulation of the geometrical properties. The changes in the topology of this nanohole array affected the intensity and the wavelength of transmission peaks. The sensitivity of the optical response to the refractive index was also investigated. The designed structure is a good candidate for use as a polarization-independent optical label-free sensor.

     

Predicting the Size of Silver Nanoparticles from Their Optical Properties

Plasmonics - In this study, localized surface plasmon resonance (LSPR) of the spherical silver nanoparticles (AgNPs) was evaluated based on experimental and theoretical viewpoints. In the...     

A Combined Spectroscopic and Theoretical Analysis of Plasmonic Silver Nanoparticle Sensor Towards Detailed Microscopic Understanding of Heavy Metal Detection

Plasmonic nanoparticles are of great importance owing to their highly responsive ‘localized surface plasmon resonance’ (LSPR) behaviour to self-agglomeration/aggregation leading to the development of various nanosensors. Herein, we demonstrated the definite self-assembly of citrate functionalized silver nanoparticles (AgNPs) into a one-dimensional linear chain in presence of charged lead ions (Pb²⁺), one of the most toxic heavy metal pollutants. We have explored detail mechanism using a variety of spectroscopic tools and electron microscopy. The self-aggregation of AgNPs leads to the generation of new LSPR modes due to coupling of nearby existing modes. The conclusion of our experimental findings is duly supported by our developed numerical modelling based on the quasi-static approximation that the generated new LSPR modes are solely due to formation of chain-like aggregation of AgNPs. We have also monitored the LSPR spectra in the presence of other metal ions; however, only Pb²⁺ found to give such unique self-assembled geometry may due to its high interaction affinity with citrate. These findings play a key role for citrate functionalised AgNPs to be used as a low cost highly selective and sensitive lead ion sensor for potential application in industrial lead pollution monitoring. We have further varied several sensor parameters such as AgNPs size, concentration, and the allowed reaction time for it to be practically implemented as an efficient lead sensor meeting the Environmental Protection Agency recommendations.

Graphical abstract

The possible sensing mechanism of citrate-functionalized silver nanoparticles towards Pb2?+?followed by unique chain-like aggregation for potential atmospheric and industrial lead pollution monitoring.

     

Seed-mediated Plasmon-driven Regrowth of Silver Nanodecahedrons (NDs)

We report the synthesis of silver nanodecahedrons (NDs) for extending the localized surface plasmon resonance (LSPR) of silver nanostructures from blue to green-orange (~590 nm), which will enable much wider application opportunities using common laser light sources. In our photo-assisted method, we use a light-emitting-diode (LED) to control regrowth of silver ND from precursor seeds. Highly uniform silver NDs are synthesized when the LED emission peak coincides with the LSPR peak of the seeds. A two-step process involving precursor self-transformation into silver nanoprisms and nanoplates, and subsequent photo-activated regrowth of silver NDs has been proposed. Surface-enhanced Raman scattering of silver NDs in different sizes has been studied, and the average enhancement factor for each size is estimated to be in the order of ~10⁶.     

Scaffold-Based Multi-nanoparticle Clusters as Tunable LSPR Substrates for SERS Applications

Tunable local surface plasmon resonance (LSPR) enhancement properties of scaffold-based multi-nanoparitcle clusters were investigated using finite-difference time-domain (FDTD) method with calculated optical spectra, near-field distribution, and average enhancement of hybrid nanostructures as slab/nanoparticls, cylinder/nanoparticles, and sphere/nanoparticles. Focusing on influence factors including surface curvature, coupling effect, and decorated particle number, several models were built for further understanding on the dominate contribution in complicate multi-particle nanostructure and to explore their potential for plasmonic enhancement applications such as surface-enhanced Raman spectroscopy (SERS), solar cells material, LSPR sensor, and nanoantenna.     

Nanostructure shape effects on response of plasmonic aptamer sensors

A localized surface plasmon resonance (LSPR) sensor surface was fabricated by the deposition of gold nanorods on a glass substrate and subsequent immobilization of the DNA aptamer, which specifically bind to thrombin. This LSPR aptamer sensor showed a response of 6‐nm λ_max shift for protein binding with the detection limit of at least 10 pM, indicating one of the highest sensitivities achieved for thrombin detection by optical extinction LSPR. We also tested the LSPR sensor fabricated using gold bipyramid, which showed higher refractive index sensitivity than the gold nanorods, but the overall response of gold bipyramid sensor appears to be 25% less than that of the gold nanorod substrate, despite the approximately twofold higher refractive index sensitivity. XPS analysis showed that this is due to the low surface density of aptamers on the gold bipyramid compared with gold nanorods. The low surface density of the aptamers on the gold bipyramid surface may be due to the effect of shape of the nanostructure on the kinetics of aptamer monolayer formation. The small size of aptamers relative to other bioreceptors is the key to achieving high sensitivity by biosensors on the basis of LSPR, demonstrated here for protein binding. The generality of aptamer sensors for protein detection using gold nanorod and gold nanobipyramid substrates is anticipated to have a large impact in the important development of sensors toward biomarkers, environmental toxins, and warfare agents. Copyright © 2013 John Wiley & Sons, Ltd.     

Gold Nanoring Arrays for Near Infrared Plasmonic Biosensing

Gold nanoring array surfaces that exhibit strong localized surface plasmon resonances (LSPR) at near infrared (NIR) wavelengths from 1.1 to 1.6 μm were used as highly sensitive real-time refractive index biosensors. Arrays of gold nanorings with tunable diameter, width, and spacing were created by the nanoscale electrodeposition of gold nanorings onto lithographically patterned nanohole array conductive surfaces over large areas (square centimeters). The bulk refractive index sensitivity of the gold nanoring arrays was determined to be up to 3,780 cm⁻¹/refractive index unit by monitoring shifts in the LSPR peak by FT-NIR transmittance spectroscopy measurements. As a first application, the surface polymerization reaction of dopamine to form polydopamine thin films on the nanoring sensor surface from aqueous solution was monitored with the real-time LSPR peak shift measurements. To demonstrate the utility of the gold nanoring arrays for LSPR biosensing, the hybridization adsorption of DNA-functionalized gold nanoparticles onto complementary DNA-functionalized gold nanoring arrays was monitored. The adsorption of DNA-modified gold nanoparticles onto nanoring arrays modified with mixed DNA monolayers that contained only 0.5 % complementary DNA was also detected; this relative surface coverage corresponds to the detection of DNA by hybridization adsorption from a 50 pM solution.

     

Plasmonic Biosensor Based on Triangular Au/Ag and Au/Ag/Au Core/Shell Nanoprisms onto Indium Tin Oxide Glass

Gold–silver core–shell triangular nanoprisms (Au/AgTNPs) were grown onto transparent indium tin oxide (ITO) thin film-coated glass substrate through a seed-mediated growth method without using peculiar binder molecules. The resulting Au/AgTNPs were characterized by scanning electron microscopy, atomic force microscopy, X-ray diffraction, UV–vis spectroscopy, and cyclic voltammograms. The peak of dipolar plasmonic resonance was located at near infrared region of ～700 nm, which showed the refractive index (RI) sensitivity of 248 nm/RIU. Moreover, thin gold shells were electrodeposited onto the surface of Au/AgTNPs in order to stabilize nanoparticles. Compared with the Au/AgTNPs, this peak of localized surface plasmon resonance (LSPR) was a little red-shift and decreased slightly in intensity. The refractive index sensitivity was estimated to be 287 nm/RIU, which showed high sensitivity as a LSPR sensing platform. Those triangular nanoprisms deposited on the ITO substrate could be further functionalized to fabricate LSPR biosensors. Results of this research show a possibility of improving LSPR sensor by using core–shell nanostructures.     

Plasmonic Properties of β-Sn Nanoparticles in Ordered and Disordered Arrangements

This work investigates the localized surface plasmon resonance (LSPR) of β-Sn also known as white tin. Recently, studies on arrays of β-Sn nanoparticles have shown that these arrays possess strong optical features caused by diffractive effects in the particle grating (Johansen et al., Phys Rev B 84:113405–113408, 2011). In the presence of the grating, the LSPR could not clearly be distinguished in the spectra. To get a better understanding of the plasmonic properties of the particles, we have now eliminated the diffractive effects by placing the particles in a random distribution. The particles were fabricated by electron beam lithography on a fused silica substrate and investigated by optical transmission measurements. In the random configuration, a clear LSPR is observed at 530 nm for particles with a diameter of 155 nm and a height of 50 nm.     

Plasmonic Perfect Absorbers for Biosensing Applications

We present a theoretical modal investigation of plasmonic perfect absorbers (PPAs) based on the localized surface plasmon resonance (LSPR) for biosensing applications. We design the PPA geometry with a layer of periodic metallic nanoparticles on one side of a dielectric substrate and a single metallic layer on the opposite side. The electromagnetic (EM) fields confine partly in the surrounding medium above the substrate and within the substrate itself. We examine the modes of the PPA geometry for a wavelength range of 600–1500 nm. The fundamental mode of the system provides perfect absorption for a wide angle of incidence 0–70°. The second-order mode shows a strong angular dependence with a sharp resonance and exhibits perfect optical absorption when the critical coupling condition for LSPR is achieved. The coupling condition depends on the size, periodicity, dielectric spacer, and the surrounding material of the system. The strong dependence on the surrounding material makes it a promising candidate for biosensing applications. We introduce a novel approach to investigate the angular dependence of the refractive index change for the PPA system. This novel technique contributes the significant attributes of the LSPR sensors, can be used for any required resonance wavelength depending on geometric design, and it also provides sensitivity analogous to the standard surface plasmon resonance (SPR) biosensors.     

A label-free immunosensor for determination of salbutamol based on localized surface plasmon resonance biosensing

We developed a localized surface plasmon resonance (LSPR)-based label-free optical biosensor for detection of salbutamol (Sal). Hollow gold nanoparticles (HGNs) which deposited on transparent indium tin oxide (ITO) film coated glass was used to sensing platform. Antibody against Sal was immobilized on HGN surface to recognize the target Sal molecules. Thus, the change of LSPR peak was proportional to the concentration of Sal in the solution. The experimental results demonstrated that the LSPR immunosensor possessed a good sensitivity and a high selectivity for Sal. The detection range for Sal was from 0.05 to 0.8 μg/mL with a correlation coefficient of 0.996. The biosensor was applied for the detection for Sal in spiked animal feed and pork liver samples, and the recoveries were in the range of 97–105 %. Therefore, it is expected that this approach may offer a new method in designing label-free LSPR immunosensor for detection of small molecules.     

Probing the Localized Surface Plasmon Field of a Gold Nanoparticle-Based Fibre Optic Biosensor

Gold nanoparticles (GNP) have been used in a variety of localized surface plasmon resonance (LSPR)-based optical sensor systems and in a variety of forms, such as colloidal suspensions, immobilized GNP on flat surfaces or optical fibres. A key parameter affecting the sensitivity of these systems is the effective depth of penetration of the surface plasmons. This study aims to determine the plasmon penetration depth in the case of an immobilized GNP-based LSPR optical biosensor. The optical biosensor used for experimentation is a U-bend fibre optic probe of 200-μm core diameter and 1.5-mm bend diameter on which GNP is immobilized. Formation of multilayered nanostructures on the immobilized GNP was used to investigate the field of the localized surface plasmons. Two multilayered nanostructures were explored in this study, viz. a polyelectrolyte multilayer formed by layer-by-layer (LBL) deposition of oppositely charged polyelectrolytes and an immunoglobulin G (IgG) multilayer formed through sequential immobilization of two mutually specific antibodies. Measurement of LSPR absorbance change with deposition of each analyte layer was used to determine the plasmon penetration depth (d _P) of the LSPR biosensor. Probing the plasmon field with an IgG multilayer gave rise to at least twofold higher d _P compared to d _P obtained from the polyelectrolyte multilayer. The effect of GNP size was also studied, and GNP of three diameters, viz. 18, 36 and 45 nm, were used. The 36-nm-diameter GNP exhibited the highest d _P. The outcomes of this study may provide leads for optimization of LSPR-based sensors for various biosensing applications.     

Self-Referencing Plasmonic Array Sensors

A self-referencing plasmonic platform is proposed and analyzed. By introducing a thin gold layer below a periodic two-dimensional nano-grating, the structure supports multiple modes including localized surface plasmon resonance (LSPR), surface plasmon resonance (SPR), and Fabry-Perot resonances. These modes get coupled to each other creating multiple Fano resonances. A coupled mode between the LSPR and SPR responses is spatially separated from the sensor surface and is not sensitive to refractive index changes in the surrounding materials or surface attachments. This mode can be used for self-referencing the measurements. In contrast, the LSPR dominant mode shifts in wavelength when the refractive index of the surrounding medium is changed. The proposed structure is easy to fabricate using conventional lithography and electron beam deposition methods. A bulk sensitivity of 429 nm/RIU is achieved. The sensor also has the ability to detect nanometer thick surface attachments on the top of the grating.

     

Theoretical Study of the Anchoring Influence on Plasmonic Resonance Tunability of Metallic Nanoparticles Embedded in a Liquid Crystal Cell

In this paper, the localized surface plasmon resonance (LSPR) peak position of an ordered gold nanoparticles array embedded in a nematic liquid crystal (LC) media is investigated using finite-difference time-domain method. The influence of the anchoring effects between nematic LC molecules and glass substrate on the shift of LSPR wavelength is taken into account, and results are compared with the case of a perfect alignment of the LC molecules.     

Real-time protein biosensor arrays based on surface plasmon resonance differential phase imaging

This paper reports the application of differential phase surface plasmon resonance (SPR) imaging in two-dimensional (2D) protein biosensor arrays. Our phase imaging approach offers a distinct advantage over the conventional angular SPR technique in terms of utilization efficiency of optical sensor elements in the imaging device. In the angular approach, each biosensor site in the biosensor array requires a linear array of optical detector elements to locate the SPR angular dip. The maximum biosensor density that a two-dimensional imaging device can offer is a one-dimensional SPR biosensor array. On the other hand, the phase-sensitive SPR approach captures data in the time domain instead of the spatial domain. It is possible that each pixel in the captured interferogram represents one sensor site, thus offering high-density two-dimensional biosensor arrays. In addition, our differential phase approach improves detection resolution through removing common-mode disturbances. Experimental results demonstrate a system resolution of 8.8 x 10(-7)RIU (refractive index unit). Real-time monitoring of bovine serum albumin (BSA)/anti-BSA binding interactions at various concentration levels was achieved using a biosensor array. The detection limit was 0.77 microg/ml. The reported two-dimensional SPR biosensor array offers a real-time and non-labeling detection tool for high-throughput protein array analysis. It may find promising applications in protein therapeutics, drug screening and clinical diagnostics.     

Localized Surface Plasmon Resonance in Gold Nanocluster Arrays on Opaque Substrates

Plasmonics - We report on the investigation of the localized surface plasmon resonance (LSPR) in periodical Au nanostructures. The arrays of Au nanoclusters and dimers were fabricated on Si and...