Shift Of Surface Plasmon Resonance Wavelength Research Articles

Advanced Integration of Glutathione-Functionalized Optical Fiber SPR Sensor for Ultra-Sensitive Detection of Lead Ions.

It is crucial to detect Pb2+ accurately and rapidly. This work proposes an ultra-sensitive optical fiber surface plasmon resonance (SPR) sensor functionalized with glutathione (GSH) for label-free detection of the ultra-low Pb2+ concentration, in which the refractive index (RI) sensitivity of the multimode-singlemode-multimode (MSM) hetero-core fiber is largely enhanced by the gold nanoparticles (AuNPs)/Au film coupling SPR effect. The GSH is modified on the fiber as the sensing probe to capture and identify Pb2+ specifically. Its working principle is that the Pb2+ chemically reacts with deprotonated carboxyl groups in GSH through ligand bonding, resulting in the formation of stable and specific chelates, inducing the variation of the local RI on the sensor surface, which in turn leads to the SPR wavelength shift in the transmission spectrum. Attributing to the AuNPs, both the Au substrates can be fully functionalized with the GSH molecules as the probes, which largely increases the number of active sites for Pb2+ trapping. Combined with the SPR effect, the sensor achieves a sensitivity of 2.32 × 1011 nm/M and a limit of detection (LOD) of 0.43 pM. It also demonstrates exceptional specificity, stability, and reproducibility, making it suitable for various applications in water pollution, biomedicine, and food safety.

L-cysteine/MoS2 modified robust surface plasmon resonance optical fiber sensor for sensing of Ferritin and IgG

L-cysteine conjugated molybdenum disulphide (MoS2) nanosheets have been covalently attached to a gold coated surface plasmon resonance (SPR) optical fiber to prepare a robust and stable sensor. Owing to the multifunctionality of the deposited nanosheet conjugate, the antibodies are also covalently conjugated in the subsequent step to realize the design of a SPR optical fiber biosensor for the two important bioanalytes namely, Ferritin and Immunoglobin G (IgG). The different stages of the biosensor preparation have been characterized and verified with microscopic and spectroscopic techniques. A uniform and stable deposition of the L-cysteine/MoS2 nanosheets has allowed the biosensor to be reused for multiple times. Unlike the peeling-off of the MoS2 coatings from the gold layer reported previously in the case of physically adsorbed nanomaterial, the herein adopted strategy addresses this critical concern. It has also been possible to use the single SPR fiber for both Ferritin and IgG bioassay experiments by regenerating the sensor and immobilizing two different antibodies in separate steps. For ferritin, the biosensor has delivered a linear sensor response (SPR wavelength shifts) in the concentration range of 50–400 ng/mL, while IgG has been successfully sensed from 50 to 250 µg/mL. The limit of detection for Ferritin and IgG analysis have been estimated to be 12 ng/mL and 7.2 µg/mL, respectively. The biosensors have also been verified for their specificity for the targeted molecule only. A uniform and stable deposition of the nanomaterial conjugate, reproducibility, regeneration capacity, a good sensitivity, and the specificity can be highlighted as some of key features of the L-cysteine/MoS2 optical fiber biosensor. The system can be advocated as a useful biosensor setup for the sensitive biosensing of Ferritin and IgG.

Design and Implementation of a Dual-Region Self-Referencing Fiber-Optic Surface Plasmon Resonance Biosensor.

The need for self-referencing is extremely important in the field of biosensing. In this manuscript, we report on the study, design, and validation of a dual-region self-referencing fiber-optic surface plasmon resonance biosensor. One region is intended to measure and monitor the binding events of the biological sample under test, while the other one is designed to be used as a reference channel to compensate for external factors, such as bulk refractive index modifications and temperature oscillations, that can negatively affect the biomolecular interaction measurement. Two different configurations for the biosensor probe are presented and investigated here, both theoretically and experimentally. First, the theoretical performance of the proposed biosensor probes, in terms of surface plasmon resonance wavelength shift, was simulated using a numerical model. Afterward, they were experimentally validated in sucrose-water solutions and showed a response to refractive index and temperature changes with sensitivities up to 2000 nm/RIU and 1.559 nm/°C, respectively. Finally, an aptamer-based bioassay and a high-resolution melting assay were successfully implemented on the two proposed configurations, demonstrating the feasibility of analyzing the binding events and measuring other external signal modifications simultaneously using the same biosensor probe.

PEI-coated Prussian blue nanocubes as pH-Switchable nanozyme: Broad-pH-responsive immunoassay for illegal additive

Nanozymes are commonly used in the construction of immunosensors, yet they are generally susceptible to pH condition, which greatly hindered their practical use. To break the limitation of pH conditions, polyethyleneimine-coated Prussian blue nanocubes (PBNCs@PEI) were synthesized as the pH-switchable nanozyme, which can show peroxidase-like and catalase-like activity in acidic and alkaline condition, respectively. Besides, the modification of PEI can largely improve the catalytic activity of PBNCs. Herein, the pH-switchable catalytic property of PBNCs@PEI was used to construct the dual-mode immunosensor for the detection of illegal additive, rosiglitazone. In acidic condition, PBNCs@PEI showed excellent peroxidase-like activity, which can trigger the colorimetric reaction of Au nanostars with TMB2+/CTAB. In alkaline condition, the catalase-like activity of PBNCs@PEI prevailed, thus the decomposition of H2O2 can generate O2 to initiate the aerobic oxidation of 4-chloro-1-naphthol (4-CN), which can decrease the fluorescence intensity of 4-CN. Based on the competitive immunoassay, both the localized surface plasmon resonance wavelength shift of Au nanostars and the fluorescence intensity change of 4-CN were quantitatively related with rosiglitazone concentration, thus shedding a new light on the construction of broad-pH-responsive immunosensor. Besides, a smart device was developed to transfer the chroma value of Au nanostars into the RSG concentration, making this sensor a promising method in on-site and point-of-care detection.

Combination of Capped Gold Nanoslit Array and Electrochemistry for Sensitive Aqueous Mercuric Ions Detection.

Label-free surface plasmon resonance (SPR) detection of mercuric ions in various aqueous solutions, using capped gold nanoslit arrays combined with electrochemical (EC) sensing technique, is demonstrated. The nanoslit arrays are fabricated on flexible cyclo-olefin polymer substrates by a nanoimprinting lithography method. The EC and SPR signals for the investigation of current responses and transmission SPR spectra are simultaneously measured during metal ions electrodeposition. Glycerol–water solution is studied to evaluate the resonant peak wavelength sensitivity (480.3 nm RIU−1) with a FOM of 40.0 RIU−1 and the obtained intensity sensitivity is 1819.9%. The ferrocyanide/ferricyanide redox couple performs the diffusion controlled electrochemical processes (R2 = 0.99). By investigating the SPR intensity changes and wavelength shifts of various mercuric ion concentrations, the optical properties are evaluated under chronoamperometric conditions. The sensors are evaluated in the detection range between 100 μM and 10 nM with a detection limit of 1 μM. The time dependence of SPR signals and the selectivity of 10 μM Hg2+ in the presence of 10 μM interfering metal ion species from Ca2+, Co2+, Ni2+, Na+, Cu2+, Pb2 + and Mn2+ are determined. The capped gold nanoslit arrays show the selectivity of Hg2+ and the EC sensing method is effectively utilized to aqueous Hg2+ detection. This study provides a label-free detection technique of mercuric ions and this developed system is potentially applicable to detecting chemicals and biomolecules.

Thymine-Functionalized Gold Nanoparticles (Au NPs) for a Highly Sensitive Fiber-Optic Surface Plasmon Resonance Mercury Ion Nanosensor.

Mercury ion (Hg2+) is considered to be one of the most toxic heavy metal ions. Once the content of Hg2+ exceeds the quality standard in drinking water, the living environment and health of human beings will be threatened and destroyed. Therefore, the establishment of simple and efficient methods for Hg2+ ion detection has important practical significance. In this paper, we present a highly sensitive and selective fiber-optic surface plasmon resonance (SPR) Hg2+ ion chemical nanosensor by designing thymine (T)-modified gold nanoparticles (Au NPs/T) as the signal amplification tags. Thymine-1-acetic acid (T-COOH) was covalently coupled to the surface of 2-aminoethanethiol (AET)-modified Au NPs and Au film by 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride/N-Hydroxysuccinimide (EDC/NHS) activation effect, respectively. In the presence of Hg2+ ions, the immobilized thymine combines specifically with Hg2+ ions, and forms an Au/thymine-Hg2+-thymine/Au (Au/T-Hg2+-T/Au) complex structure, leading to a shift in SPR wavelength due to the strong electromagnetic couple between Au NPs and Au film. Under optimal conditions, the proposed sensor was found to be highly sensitive to Hg2+ in the range of 80 nM–20 µM and the limit of detection (LOD) for Hg2+ was as low as 9.98 nM. This fiber-optic SPR sensor afforded excellent selectivity for Hg2+ ions against other heavy metal ions such as Fe3+, Cu2+, Ni2+, Ba2+, K+, Na+, Pb2+, Co2+, and Zn2+. In addition, the proposed sensor was successfully applied to Hg2+ assay in real environmental samples with excellent recovery. Accordingly, considering its simple advantages, this novel strategy provides a potential platform for on-site determination of Hg2+ ions by SPR sensor.

Enhanced Surface Plasmon Resonance Wavelength Shifts by Molecular Electronic Absorption in Far- and Deep-Ultraviolet Regions

In this study, surface plasmon resonance (SPR) wavelength shifts due to molecular electronic absorptions in the far-ultraviolet (FUV, < 200 nm) and deep-ultraviolet (DUV, < 300 nm) regions were investigated by attenuated total reflectance (ATR) spectroscopy. Due to the strong absorption in the DUV region, N,N-dimethylformamide (DMF) significantly increased the SPR wavelength shift of Al film. On the other hand, no such shift enhancement was observed in the visible region for Au film because DMF does not have absorbance compared to non-absorbing materials such as water and alcohols. The enhanced SPR wavelength shift, caused by the overlap between SPR and molecular resonance wavelengths in FUV-DUV region, is expected to result in high sensitivity for resonant materials.

The temperature responsive mechanism of fiber surface plasmon resonance sensor

The temperature responsive mechanism of the optical fiber Surface Plasmon Resonance (SPR) sensor is analyzed. It is found that, both the gold film and the fiber core change with increasing temperature and affect the temperature sensitivity of the SPR sensor, but the main factor of the intrinsic temperature sensitivity of the sensor is the temperature dependent SPR response of the gold coating. The gold film plasma frequency plays a critical role in the temperature response mechanism of the sensor. Experimental and simulation results show that the SPR wavelength shift due to the change of the gold film temperature contributes 19.6 % to the total, as the sensor surrounded with ethanol and the environment temperature increases from 0°C to 50°C. The reason is that the plasma frequency of the gold film rises significantly as the external temperature increases. The rising rate of plasma frequency with temperature is related to the morphology and the deposition method of the gold film. This result has provided a novel insight on the physical properties of optical fiber SPR sensors and has improved the capability of SPR sensors for measuring signals in a temperature-changing environment.

Plasmonic Fiber-Optic Photothermal Anemometers With Carbon Nanotube Coatings

We propose and demonstrate an ultra-sensitive plasmonic fiber-optic hot-wire anemometer. This instrument comprises a highly tilted fiber Bragg grating-assisted surface plasmon resonance (SPR) sensor, which is coated with carbon nanotubes as the photothermal conversion element. The carbon nanotubes on the sensor surface efficiently convert light from the heating laser, of which wavelength matched to the SPR window, into heat, thereby setting the sensor in an elevated temperature state. Air flow draws away surface heat, thus inducing both a strong SPR wavelength shift and power modulation. Using this anemometer, we experimentally achieve a dynamic range of 0.05 to 0.65 m/s for wind speed measurement. Furthermore, we demonstrate real-time monitoring of wind speed by measuring the intensity of the heating laser. This sensor is simple and robust in structure. It has a wide range of potential applications in both scientific research and industrial production.

Investigation of sequential thermal annealing effect on Cu-C70 nanocomposite thin film

Cu-C70 nanocomposite thin film is synthesized via thermal co-evaporation method. The atomic concentration of Cu in the thin film is found to be ~4.5 at.% using Rutherford backscattering spectroscopy. Sequential thermal annealing is performed in an inert atmosphere (in presence of Ar) at various temperatures. Surface plasmon resonance (SPR) is spotted at ~585 nm for the sample annealed at 300 °C and the SPR peak is shifted towards ~621 nm for the sample annealed at 400 °C. In order to determine the modifications arising in the structure of fullerene C70 matrix due to annealing, Raman spectroscopy is used. At the highest temperature of 400 °C, the high-intensity Raman active modes of fullerene C70 can still be observed which shows that fullerene C70 is not completely transformed into amorphous carbon upto this temperature. Transmission electron microscopy is performed to determine the size of particles which is obtained ~35 nm for the sample annealed at 400 °C. The red shift in SPR wavelength at 400 °C is ascribed to the growth of Cu nanoparticles.

Biomolecular charges influence the response of surface plasmon resonance biosensors through electronic and ionic mechanisms

Surface plasmon resonance (SPR) biosensors have become an important label-free optical biomolecular sensing technology and a “gold standard” for retrieving information on the kinetics of biomolecular interactions. Even though biomolecules typically contain an abundance of easily ionizable chemical groups, there is a gap in understanding of whether (and how) the electrostatic charge of a biomolecular system influences the SPR biosensor response. In this work we show that negative static charge present in a biomolecular layer on the surface of an SPR sensor results in significant SPR spectral shifts, and we identify two major mechanisms responsible for such shifts: 1) the formation of an electrical double layer (ionic mechanism), and 2) changes in the electron density at the surface of a metal (electronic mechanism). We show that under low ionic strength conditions, the electronic mechanism is dominant and the SPR wavelength shift is linearly proportional to the surface concentration of biomolecular charges. At high ionic strength conditions, both electric and ionic mechanisms contribute to the SPR wavelength shift. Using the electronic mechanism, we estimated the pKa of surface-bound carboxylic groups and the relative concentration of the carboxyl-terminated alkanethiols in a binary self-assembled monolayer of alkanethiols. The reported sensitivity of SPR to surface charge is especially important in the context of biomolecular sensing. Moreover, it provides an avenue for the application of SPR sensors for fast, label-free determination of the net charge of a biomolecular coating, which is of interest in material science, surface chemistry, electrochemistry, and other fields.

Far- and deep-ultraviolet surface plasmon resonance sensors working in aqueous solutions using aluminum thin films

Surface plasmon resonance (SPR) sensors detect refractive index changes on metal thin films and are frequently used in aqueous solutions as bio- and chemical-sensors. Recently, we proposed new SPR sensors using aluminum (Al) thin films that work in the far- and deep-ultraviolet (FUV-DUV, 120–300 nm) regions and investigated SPR properties by an attenuated total reflectance (ATR) based spectrometer. The FUV-DUV-SPR sensors are expected to have three advantages compared to visible-SPR sensors: higher sensitivity, material selectivity, and surface specificity. However, in this study, it was revealed that the Al thin film on a quartz prism cannot be used as the FUV-DUV-SPR sensor in water solutions. This is because its SPR wavelength shifts to the visible region owing to the presence of water. On the other hand, the SPR wavelength of the Al thin film on the sapphire prism remained in the DUV region even in water. In addition, the SPR wavelength shifted to longer wavelengths with increasing refractive index on the Al thin film. These results mean that the Al thin film on the sapphire prism can be used as the FUV-DUV-SPR sensor in solutions, which may lead to the development of novel and sophisticated SPR sensors.

Design and simulation of high sensitive cylindrical nanogear shell sensors according to localized surface plasmon resonance

Localized surface plasmon resonance wavelength depends on intrinsic and environmental factors of nanoparticles. One of the most important factors is the shape of nanoparticles. The effects of nanoparticles shape on the surface plasmon resonance wavelength shift are simulated and investigated. We have observed that the sensitivity of single cylindrical nanoshell with inner and outer radiuses of 20 and 25nm and length of 70nm is 509nm/RIU while the sensitive nature of nanogear with the same size is 603nm/RIU. It is nearly four times the sensitivity of solid spherical nanoparticles and two times the sensitivity of solid nanorods.

Effect of Voltage Bias at MEH-PPV Layer on SPR Wavelength observed during in-situ Measurement Method in Polymer Light Emitting Diode

The shifting of surface plasmon resonance (SPR) wavelength has been observed during in situ measurement in polymer light emitting diode (pLED). Examination is performed using an pLED sample which has an ITO/PEDOT:PSS/MEH-PPV/Au structure. When the voltage bias is increased from 0 to 9 volt the SPR wavelength shifts from 612 nm to 628 nm and the absorption curve shifts to lower absorbance value. From the theoretical analysis, it can be understood that the change of the SPR dip and the absorption curves correspond to the change of dielectric constant of the MEH-PPV layer. These results show that SPR wavelength depends on the metal and air dielectric constant as well as on the MEH-PPV layer. These results also imply that the SPR wavelength being evaluated can be controlled by varying the voltage bias.

SURFACE PLASMON RESONANCE SENSOR OF SILVER FILM BASED ON KRETCHMANN CONFIGURATION

Performance of a surface plasmon resonance (SPR) sensor based on Kretchmann configuration for silver (Ag) film is evaluated via theoretical simulation. The film thickness and incident angle are varied to obtain the SPR wavelength in the range of 500-550 nm. Shift of SPR wavelength with refractive index of the dielectric defines the sensitivity whereas the resolution is obtained from the ratio of the instrumental resolution to the sensitivity. The SPR sensor shows increasing sensitivity for thicker film however the absorption magnitudes of such films are high and unfavourable for data acquisition. Film thickness of 45 nm and 50 nm which has good sensitivity and resolution with high absorbance magnitude of the SPR wavelength is the best thickness to be employed for sensing purpose.

Tapered Fiber-Optic Based Surface Plasmon Resonance Sensor

We propose a tapered fiber-optic based surface plasmon resonance (SPR) sensor. The plasmonic sensing is designed by coating the waist of tapered fiber-optic with gold. The transmission spectrum of SPR wavelength were investigated by 2D finite element method (FEM). The calculation shows that the dips of the resonance wavelength shift toward long wave direction with the thickness of gold film decreasing. And increasing the diameters of the waist core of tapered fiber-optic also makes the resonance wavelength shift long wave direction. Furthermore, changing the refractive index of the external samples from 1.333 to 1.343 with step of ~0.002, the SPR wavelength shifts linearly from 575.05nm to 472.5nm. Owing to its compact and simple configuration, it also provides a feasible program for the refractive index high sensitivity detection.Keywords: surface plasmon resonance (SPR); tapered fiber-optic sensor; surface plasma; finite element method (FEM); optical fiber sensor

Scaling of the Surface Plasmon Resonance in Gold and Silver Dimers Probed by EELS

The dependence of surface plasmon coupling on the distance between two nanoparticles (dimer) is the basis of nanometrology tools such as plasmon rulers. Application of these nanometric rulers requires an accurate description of the scaling of the surface plasmon resonance (SPR) wavelength with distance. Here, we have applied electron energy-loss spectroscopy (EELS) and scanning transmission electron microscopy (STEM) imaging to investigate the relationship between the SPR wavelength of gold and silver nanosphere dimers (radius R) and interparticle distance (d) in the range 0.1R < d < R. The choice of EELS enables probing the SPRs of individual dimers, whose dimensions and separation distances are measured in situ with subnanometer resolution using STEM. We find that the decaying exponential description of the fractional SPR wavelength shift with d/2R holds valid only over a limited range of d. Instead, within the range 0.1R < d < R the fractional SPR wavelength shift is found to be related to (2R/d)n, wit...

Detection of HLA-B⁎27 gene using a spectral plasmon resonance imaging system

Detection of HLA-B⁎27 gene is clinically important due to its strong association with diseases, such as ankylosing spondylitis. Nucleic acid-based biosensors represent a promising clinical tool for gene diagnosis. Surface plasmon resonance (SPR) can be used to monitor DNA–DNA hybridization in real-time and without any prior labeling step. Here, a self-built HLA-B⁎27 positive PCR products spectral SPR imaging system was used for multichannel direct-detection of a specific sequence of the HLA-B⁎27 gene. Thiol-labeled single-stranded oligonucleotide probes, which were proved to be superior to amine-labeled probes in immobilization, were immobilized onto the surfaces of the gold spots on the sensor chip to target the specific sequence in the HLA-B⁎27 gene in blood. SPR measurements were performed with different concentrations of synthetic target DNA sequence. The calibration curve of synthetic target sequence showed a good linear relationship between the concentration of the synthetic target sequence and the shift of the SPR wavelength from 10nM to 500nM with a detection limit of 5nM. The HLA-B⁎27 gene was isolated from human whole blood and amplified using polymerase chain reaction (PCR). PCR products were measured using the SPR imaging system. HLA-B⁎27 positive PCR products showed significant SPR wavelength shift, while synthetic non-complementary sequence and negative PCR products showed no significant SPR wavelength shift. The method is high-specific, high-throughput and label-free.

Gradually shifting surface plasmon resonance by controlling the diameter of a nanohole structure by self-assembly

A new fabrication method for a surface plasmon resonance (SPR) device with a gradual SPR shift—namely, using a nanostructure self-assembled by using a mixed block copolymer as a template—was developed. By this method, it was demonstrated that the diameter of a self-assembled nanohole can be controlled by changing the film thickness of a mixed block copolymer. It was also demonstrated that SPR wavelength shift can be controlled according to the nanohole structure (with diameter controlled according to film thickness). An actual SPR device with a gradually shifted SPR wavelength was fabricated, and it was confirmed that this SPR device can detect refractive-index change in its surroundings. This device has the potential to expand the application of SPR devices.

Design considerations for surface plasmon resonance-based fiber-optic detection of human blood group

A fiber-optic surface plasmon resonance (SPR) sensor for the detection of human blood groups is proposed. Previous experimental results describing the wavelength-dependent refractive index variation of multiple samples of different blood groups are considered for theoretical calculations. The spectral interrogation method, along with silica fiber and silver layer, is considered. The sensor's performance is closely analyzed in terms of shift in SPR wavelength and SPR curve width in order to optimize the design parameters for a reliable and accurate blood-group identifier. The sensor design parameters include silver layer thickness, fiber core diameter, sensing region length, and temperature variation. The results are explained in terms of light coupling and plasmon resonance condition. The proposed sensing probe is able to provide high sensitivity and accuracy of blood-group detection, thereby opening an easy and reliable window for medical applications.