Experimental studies on the sensitivity of the propagating and localized surface plasmon resonance-based tapered fiber optic refractive index sensors.

In the present study, the sensitivities of the fiber optic propagating surface plasmon resonance (SPR) and localized surface plasmon resonance (LSPR)-based refractive index sensors have been evaluated experimentally for a tapered probe of different taper ratio. The tapering of the fiber probe has been carried out via a heating and stretching technique. The SPR probe has been fabricated by coating a thin film of silver over the core of the tapered optical fiber, while the LSPR probe has been prepared by the coating of the gold nanoparticles over the core of the tapered optical fiber. The increase in the taper ratio increases the sensitivity of both kinds of the probes. The experimentally obtained sensitivity has been compared with the sensitivity of the SPR-based fiber optic refractive index sensors fabricated using various techniques and reported in the literature.

Carbon-Based Nanomaterials for Plasmonic Sensors: A Review.

The surface plasmon resonance (SPR) technique is a remarkable tool, with applications in almost every area of science and technology. Sensing is the foremost and majorly explored application of SPR technique. The last few decades have seen a surge in SPR sensor research related to sensitivity enhancement and innovative target materials for specificity. Nanotechnological advances have augmented the SPR sensor research tremendously by employing nanomaterials in the design of SPR-based sensors, owing to their manifold properties. Carbon-based nanomaterials, like graphene and its derivatives (graphene oxide (GO)), (reduced graphene oxide (rGO)), carbon nanotubes (CNTs), and their nanocomposites, have revolutionized the field of sensing due to their extraordinary properties, such as large surface area, easy synthesis, tunable optical properties, and strong compatible adsorption of biomolecules. In SPR based sensors carbon-based nanomaterials have been used to act as a plasmonic layer, as the sensitivity enhancement material, and to provide the large surface area and compatibility for immobilizing various biomolecules, such as enzymes, DNA, antibodies, and antigens, in the design of the sensing layer. In this review, we report the role of carbon-based nanomaterials in SPR-based sensors, their current developments, and challenges.

Ultrasensitive, highly selective, and real-time detection of protein using functionalized CNTs as MIP platform for FOSPR-based biosensor.

A facile approach is presented for the detection of bovine serum albumin (BSA), based on fiber optic surface plasmon resonance (FOSPR) combined with molecular imprinting (MI). The probe is fabricated by exploiting the plasmonic property of silver thin film and vinyl-functionalised carbon nanotube-based MIP platform. BSA template molecules are imprinted on the MIP layer coated over multi-walled carbon nanotubes to ensure high specificity of the probe in the interfering environments. In addition, FOSPR endorses the sensor capability of real-time and remote sensing along with very high sensitivity due to the use of nanostructured MI platform. The response of the probe is considered in terms of the absorbance spectrum recorded for various concentrations of BSA. The sensor shows a wide dynamic range of 0-350 ng l-1 with a considerably linear response up to 100 ng l-1 in the peak absorbance wavelength with BSA concentration. A highest sensitivity of 0.862 nm per ng l-1 is achieved for the lowest concentration of BSA and it decreases with the increase in BSA concentration. The performance of the present sensor is compared with those reported in the literature in terms of the limit of detection. It is found that the probe possesses a lowest LOD of 0.386 ng l-1 in addition to other advantages such as real-time online monitoring, high sensitivity, high specificity, and remote sensing.

Integrating nanohybrid membranes of reduced graphene oxide: chitosan: silica sol gel with fiber optic SPR for caffeine detection.

Caffeine is the most popular psychoactive drug consumed in the world for improving alertness and enhancing wakefulness. However, caffeine consumption beyond limits can result in lot of physiological complications in human beings. In this work, we report a novel detection scheme for caffeine integrating nanohybrid membranes of reduced graphene oxide (rGO) in chitosan modified silica sol gel (rGO: chitosan: silica sol gel) with fiber optic surface plasmon resonance. The chemically synthesized nanohybrid membrane forming the sensing route has been dip coated over silver coated unclad central portion of an optical fiber. The sensor works on the mechanism of modification of dielectric function of sensing layer on exposure to analyte solution which is manifested in terms of red shift in resonance wavelength. The concentration of rGO in polymer network of chitosan and silica sol gel and dipping time of the silver coated probe in the solution of nanohybrid membrane have been optimized to extricate the supreme performance of the sensor. The optimized sensing probe possesses a reasonably good sensitivity and follows an exponentially declining trend within the entire investigating range of caffeine concentration. The sensor boasts of an unparalleled limit of detection value of 1.994 nM and works well in concentration range of 0-500 nM with a response time of 16 s. The impeccable sensor methodology adopted in this work combining fiber optic SPR with nanotechnology furnishes a novel perspective for caffeine determination in commercial foodstuffs and biological fluids.

Surface plasmon resonance based fiber optic trichloroacetic acid sensor utilizing layer of silver nanoparticles and chitosan doped hydrogel.

In this study, we report a silver nanoparticles/chitosan doped hydrogel-based fiber optic sensor for the detection of trichloroacetic acid (TCA). The sensor is based on the combined phenomenon of localized and propagating surface plasmons. The sensing relies on the interaction of TCA with silver nanoparticles (AgNP) which results in the electron transfer between the negative group of TCA and positive amino group of AgNP stabilizer (chitosan). This alters the mechanical properties/refractive index of the AgNP embedded hydrogel matrix as well as the refractive index of the AgNP. The change in refractive index of both in turn changes the effective refractive index of the nanocomposite hydrogel layer which can be determined using the Maxwell-Garnet Theory. Four stage optimization of the probe fabrication parameters is performed to obtain the best performance of the sensing probe. The sensor operates in the TCA concentration range 0-120 µm which is harmful for the humans and environment. The shift in peak extinction wavelength observed for the same TCA concentration range is 42 nm. The sensor has the linearity range for the TCA concentration range of 40-100 µm. The sensor possesses high sensitivity, selectivity and numerous other advantages such as ease of handling, quick response, modest cost and capability of online monitoring and remote sensing.

A localized and propagating SPR, and molecular imprinting based fiber-optic ascorbic acid sensor using an in situ polymerized polyaniline-Ag nanocomposite.

We report a successful approach for the fabrication and characterization of a fiber-optic sensor for ascorbic acid (AA) detection, using a molecularly imprinted polyaniline-Ag (PANI-Ag) nanocomposite layer based on the combined phenomena of surface plasmon resonance (SPR) and localized SPR (LSPR). The PANI-Ag nanocomposite is synthesized by an in situ polymerization process and AA imprints are prepared on the polymeric composite. The confirmation of the PANI-Ag nanocomposite and AA imprinting is performed using various characterization methods such as x-ray diffraction (XRD), UV-vis, Fourier transform infrared spectroscopy and scanning electron microscopy. From XRD, the size of Ag nanoparticles is analyzed. The absorbance spectra are recorded for samples of different concentrations of AA around the sensing region of the probe. An increase in peak absorbance wavelength with the increase in AA concentration is observed with a linear response for the concentration range from 10(-8) M to 10(-6) M. The sensor possesses a high sensitivity of 45.1 nm log(-1) M near an AA concentration of 10(-8) M. The limit of detection (LOD) and limit of quantification of the sensor are found to be 7.383 × 10(-11) M and 4.16 × 10(-10) M, respectively. The LOD of the sensor is compared to studies reported in the literature and is found to be the lowest. The sensor possesses several other advantages such as cost effectiveness, selectivity, and low response time (<5 s), along with abilities of remote sensing and online monitoring.

Tuning the field distribution and fabrication of an Al@ZnO core-shell nanostructure for a SPR-based fiber optic phenyl hydrazine sensor.

We report the fabrication and characterization of a surface plasmon resonance (SPR)-based fiber optic sensor that uses coatings of silver and aluminum (Al)-zinc oxide (ZnO) core-shell nanostructure (Al@ZnO) for the detection of phenyl hydrazine (Ph-Hyd). To optimize the volume fraction (f) of Al in ZnO and the thickness of the core-shell nanostructure layer (d), the electric field intensity along the normal to the multilayer system is simulated using the two-dimensional multilayer matrix method. The Al@ZnO core-shell nanostructure is prepared using the laser ablation technique. Various probes are fabricated with different values of f and an optimized thickness of core-shell nanostructure for the characterization of the Ph-Hyd sensor. The performance of the Ph-Hyd sensor is evaluated in terms of sensitivity. It is found that the Ag/Al@ZnO nanostructure core-shell-coated SPR probe with f = 0.25 and d = 0.040 µm possesses the maximum sensitivity towards Ph-Hyd. These results are in agreement with the simulated ones obtained using electric field intensity. In addition, the performance of the proposed probe is compared with that of probes coated with (i) Al@ZnO nanocomposite, (ii) Al nanoparticles and (iii) ZnO nanoparticles. It is found that the probe coated with an Al@ZnO core-shell nanostructure shows the largest resonance wavelength shift. The detailed mechanism of the sensing (involving chemical reactions) is presented. The sensor also manifests optimum performance at pH 7.

Surface Plasmon Resonance-Based Fiber Optic Sensors Utilizing Molecular Imprinting.

Molecular imprinting is earning worldwide attention from researchers in the field of sensing and diagnostic applications, due to its properties of inevitable specific affinity for the template molecule. The fabrication of complementary template imprints allows this technique to achieve high selectivity for the analyte to be sensed. Sensors incorporating this technique along with surface plasmon or localized surface plasmon resonance (SPR/LSPR) provide highly sensitive real time detection with quick response times. Unfolding these techniques with optical fiber provide the additional advantages of miniaturized probes with ease of handling, online monitoring and remote sensing. In this review a summary of optical fiber sensors using the combined approaches of molecularly imprinted polymer (MIP) and the SPR/LSPR technique is discussed. An overview of the fundamentals of SPR/LSPR implementation on optical fiber is provided. The review also covers the molecular imprinting technology (MIT) with its elementary study, synthesis procedures and its applications for chemical and biological anlayte detection with different sensing methods. In conclusion, we explore the advantages, challenges and the future perspectives of developing highly sensitive and selective methods for the detection of analytes utilizing MIT with the SPR/LSPR phenomenon on optical fiber platforms.

Versatile SERS sensing based on black silicon.

Black Si (b-Si) with gold or silver metal coating has been shown to be an extremely effective substrate for surface-enhanced Raman scattering (SERS). Here, we demonstrate that it is also a highly versatile SERS platform, as it supports a wide range of surface functionalizations. In particular, we report the use of a molecularly imprinted polymer (MIP) coating and a hydrophobic coating on b-Si to establish two different sensing modalities. First, using a MIP layer on Au-coated b-Si, we show selective sensing of two closely related varieties of tetracycline. Second, a hydrophobic coating was used to concentrate the analyte adsorbed on gold colloidal nanoparticles, thus increasing the sensitivity of the measurement by an order of magnitude. In this experiment, Au nanoparticles and analyte were mixed just before SERS measurements and were concentrated by drop-drying on the super-hydrophobic b-Si. These approaches are promising for SERS measurements that are sensitive to the aging of bare plasmonic metal-coated substrates.

Surface plasmon resonance based fiber optic detection of chlorine utilizing polyvinylpyrolidone supported zinc oxide thin films.

A highly sensitive chlorine sensor for an aqueous medium is fabricated using an optical fiber surface plasmon resonance (OFSPR) system. An OFSPR-based chlorine sensor is designed with a multilayer-type platform by zinc oxide (ZnO) and polyvinylpyrollidone (PVP) film morphology manipulations. Among all the methodologies of transduction reported in the field of solid state chemical and biochemical sensing, our attention is focused on the Kretschmann configuration optical fiber sensing technique using the mechanism of surface plasmon resonance. The optical fiber surface plasmon resonance (SPR) chlorine sensor is developed using a multimode optical fiber with the PVP-supported ZnO film deposited over a silver-coated unclad core of the fiber. A spectral interrogation mode of operation is used to characterize the sensor. In an Ag/ZnO/PVP multilayer system, the absorption of chlorine in the vicinity of the sensing region is performed by the PVP layer and the zinc oxide layer enhances the shift in resonance wavelength. It is, experimentally, demonstrated that the SPR wavelength shifts nonlinearly towards the red side of the visible region with an increase in the chlorine concentration in an aqueous medium while the sensitivity of the sensor decreases linearly with an increase in the chlorine concentration. As the proposed sensor utilizes an optical fiber, it possesses the additional advantages of fiber such as less signal degradation, less susceptibility to electromagnetic interference, possibility of remote sensing, probe miniaturization, probe re-usability, online monitoring, small size, light weight and low cost.

Surface plasmon resonance-based fiber-optic hydrogen gas sensor utilizing palladium supported zinc oxide multilayers and their nanocomposite.

We analyze surface plasmon resonance-based fiber-optic sensor for sensing of small concentrations of hydrogen gas in the visible region of the electromagnetic spectrum. One of the two probes considered has multilayers of zinc oxide (ZnO) and palladium (Pd) while the other has layer of their composite over a silver coated unclad core of the fiber. The analysis is carried out for different volume fractions of palladium nanoparticles dispersed in zinc oxide host material in the nanocomposite layer. For the analysis, a Maxwell-Garnett model is adopted for calculating the dielectric function of a ZnO:Pd nanocomposite having nanoparticles of dimensions smaller than the wavelength of radiation used. The effects of the volume fraction of the nanoparticles in the nanocomposite and the thickness of the nanocomposite layer on the figure of merit of the sensor have been studied. The film thickness of the layer and the volume fraction of nanoparticles in the ZnO:Pd nanocomposite layer have been optimized to achieve the maximum value of the figure of merit of the sensor. It has been found that the figure of merit of the sensing probe coated with ZnO:Pd nanocomposite is more than twofold of the sensing probe coated with multilayers of Pd and ZnO over a silver coated unclad core of the fiber; hence, the sensor with a nanocomposite layer works better than that with multilayers of zinc oxide and palladium. The sensor can be used for online monitoring and remote sensing of hydrogen gas.

Fiber-optic ammonia sensor using Ag/SnO(2) thin films: optimization of thickness of SnO(2) film using electric field distribution and reaction factor.

A highly sensitive ammonia gas sensor exploiting the gas sensing characteristics of tin oxide (SnO2) has been reported. The methodology of the sensor is based on the phenomenon of surface plasmon resonance (SPR) with a fiber-optic probe consisting of coatings of silver as a plasmonic material and SnO2 as the sensing layer. The sensing principle relies on the change in refractive index of SnO2 upon its reaction with ammonia gas. The capability of the sensor has been tested for a 10 to 100 ppm concentration range of ammonia gas. To enhance the sensitivity, probes with different thicknesses of SnO2 have been fabricated and characterized for ammonia sensing. It has been found that at a particular thickness the sensitivity is highest. The reason for the highest sensitivity at a particular thickness has been evinced theoretically. The electromagnetic field distribution for the multilayer structure of the probe reveals the enhancement of the evanescent field at the tin oxide-ammonia gas interface, which in turn manifests the highest shift in resonance wavelength at a particular thickness. The selectivity of the probe has been tested for various gases, and it has been found to be most accurate for the sensing of ammonia. A sensor utilizing optical fiber, the SPR technique, and metal oxide as sensing element combines the advantages of a miniaturized probe, online monitoring, and remote sensing on one hand and stability, high sensitivity and selectivity, ruggedness, and low cost on the other.

A novel approach for simultaneous sensing of urea and glucose by SPR based optical fiber multianalyte sensor.

A novel design is presented for the sensing of urea and glucose simultaneously by surface plasmon resonance (SPR) based optical fiber multianalyte sensor using gel entrapment technique in a fluid for biomedical applications. Sensing surfaces are prepared by coating of different metals and high index dielectric over-layers (silver and silicon in channel 1 and copper and tin-oxide in channel 2) over two small and well separated unclad portions of an optical fiber. Enzymes urease and glucose oxidase are immobilized over respective surfaces using gel entrapment method for the sensing of urea and glucose, respectively. Wavelength interrogation technique is used for the calibration of the sensor. The concentration of urea and glucose are selected in the range 0-180 mM and 0-260 mg dl(-1), respectively, to mimic the physiological range of urea and glucose in human blood. Mixed solutions of urea and glucose with varying concentrations are prepared in buffer solution for the calibration of the sensor. The resonance wavelengths are determined corresponding to two channels responding independently to the interaction of analytes in solution on sensing channels. It is observed that the resonance wavelengths in the case of both the sensing channels decrease with the increasing concentrations of urea and glucose in solutions. The sensor gives 8.51 nm and 13.04 nm total shifts in resonance wavelength for 0 mM to 180 mM urea and 0 mg dl(-1) to 260 mg dl(-1) glucose concentrations in a sample, respectively. The advantages of the present sensor are cascaded design with multiple sensing channels on a single platform, inexpensive, simultaneous sensing of two parameters, possibility of online monitoring and remote sensing.

Surface plasmon resonance based fiber optic pH sensor utilizing Ag/ITO/Al/hydrogel layers.

The fabrication and characterization of a surface plasmon resonance based pH sensor using coatings of silver, ITO (In2O3:SnO2), aluminium and smart hydrogel layers over an unclad core of an optical fiber have been reported. The silver, aluminium and ITO layers were coated using a thermal evaporation technique, while the hydrogel layer was prepared using a dip-coating method. The sensor works on the principle of detecting changes in the refractive index of the hydrogel layer due to its swelling and shrinkage caused by changes in the pH of the fluid surrounding the hydrogel layer. The sensor utilizes a wavelength interrogation technique and operates in a particular window of low and high pH values. Increasing the pH value of the fluid causes swelling of the hydrogel layer, which decreases its refractive index and results in a shift of the resonance wavelength towards blue in the transmitted spectra. The thicknesses of the ITO and aluminium layers have been optimized to achieve the best performance of the sensor. The ITO layer increases the sensitivity while the aluminium layer increases the detection accuracy of the sensor. The proposed sensor possesses maximum sensitivity in comparison to the sensors reported in the literature. A negligible effect of ambient temperature in the range 25 °C to 45 °C on the performance of the sensor has been observed. The additional advantages of the sensor are short response time, low cost, probe miniaturization, probe re-usability and the capability of remote sensing.

Optical fiber sensor for the detection of tetracycline using surface plasmon resonance and molecular imprinting.

We present a simple and highly selective optical fiber sensor for the detection of tetracycline in foodstuffs by using the combination of surface plasmon resonance (SPR) and a molecular imprinted polymer (MIP) matrix. The sensor is fabricated first by coating a thin film of silver metal over the unclad portion of an optical fiber, and then preparing a molecular imprinting of the target molecules over the metal coated region. The MIP creates several binding sites/nano-cavities which have the complementary shape and functional groups of the target molecules on its surface. The sensor works on the wavelength modulation scheme in which the shift in resonance wavelength is measured with respect to the change in tetracycline concentration. Two kinds of tetracycline, tetracycline hydrochloride (TC) and oxy-tetracycline hydrochloride (OTC) have been selected as the imprinting molecules because these possess similar structures. The presence of tetracycline samples in the vicinity of the sensing region causes the interaction between binding sites and target molecules which results in the change in the dielectric properties of the sensing surface, causing the shift in the SPR spectrum towards the red region. The selectivity of the sensor for dissimilar compounds, and cross-selectivity between TC and OTC, has been tested. The reusability of the sensor has also been checked. The present sensor is suitable for commercialization for the detection of tetracycline in food as it has several advantageous features such as low cost, ease of handling, a miniaturized probe, fast response, high selectivity, reusability and the possibility of online monitoring and remote sensing.

Surface plasmon resonance-based fiber optic hydrogen sulphide gas sensor utilizing Cu-ZnO thin films.

We report an experimental study on a surface plasmon resonance (SPR)-based fiber optic hydrogen sulphide gas sensor with a thin metal oxide (zinc oxide (ZnO)) layer as the additional layer. This zinc oxide layer is grown over the copper layer to support surface plasmons at the metal-dielectric interface at room temperature. The wavelength interrogation mode of operation has been used to characterize the sensor. The thin film of zinc oxide over the copper film was deposited on the unclad portion of the fiber by the thermal evaporation technique. Experiments were performed for the detection of concentrations of hydrogen sulphide gas varying from 0 to 100 ppm around the probe. The unpolarized light from a polychromatic source is launched from one end of the fiber and the corresponding SPR spectrum is recorded at the other end. The recorded SPR spectrum shows a shift in the resonance wavelength on a change in the hydrogen sulphide gas concentration, which is considered as a detectable signal for the characterization of the sensor. Further, the optimization of the performance of the sensor was achieved by varying the thickness of the zinc oxide film. The sensor possesses a very fast response time and high sensitivity. Since the sensor utilizes optical fibers it has additional advantages of remote sensing, online monitoring, light weight and low cost.

Recent Advances in Silver Nanostructured Substrates for Plasmonic Sensors.

Noble metal nanostructures are known to confine photon energies to their dimensions with resonant oscillations of their conduction electrons, leading to the ultrahigh enhancement of electromagnetic fields in numerous spectroscopic methods. Of all the possible plasmonic nanomaterials, silver offers the most intriguing properties, such as best field enhancements and tunable resonances in visible-to-near infrared regions. This review highlights the recent developments in silver nanostructured substrates for plasmonic sensing with the main emphasis on surface plasmon resonance (SPR) and surface-enhanced Raman spectroscopy (SERS) over the past decade. The main focus is on the synthesis of silver nanostructured substrates via physical vapor deposition and chemical synthesis routes and their applications in each sensing regime. A comprehensive review of recent literature on various possible silver nanostructures prepared through these methodologies is discussed and critically reviewed for various planar and optical fiber-based substrates.

Portable fiber-optic SPR platform for the detection of NS1-antigen for dengue diagnosis.

Here, we present a portable, selective and cost-effective fiber-optic surface plasmon resonance (SPR) based platform for early detection of Dengue virus. NS1 protein was targeted as the biomarker of dengue. Antibody-antigen specific binding was exploited for NS1 antigen detection. The binding of antibody was assisted by a self-assembled monolayer of alkanethiols on the surface of silver-coated unclad fiber. A wavelength interrogation mode of SPR was utilized to detect NS1 antigen in the dynamic range of 0.2-2.0 µg/ml. The 40 nm thick silver coated optical fiber exhibited resonance wavelength around 500 nm and change in resonance wavelength was monitored for each attachment step on the fiber. The sensitivity at the lowest concentration of NS1 antigen was found to be 54.7 nm/(µg/ml). The limit of detection of the sensor was found to be 0.06 µg/ml, which lies in the physiological range of NS1 protein present in the infected blood, hence the present technique may provide a very early detection advantage. Real blood serum samples were also successfully tested on the set-up, confirming compatibility with the conventional methods. The presented field-deployable platform has wide applications in mass monitoring of dengue, such as during outbreaks and epidemics.

Surface-plasmon-resonance-based fiber-optic refractive index sensor: sensitivity enhancement.

We have experimentally studied the surface plasmon resonance (SPR)-based fiber-optic refractive index sensor incorporating a high-index dielectric layer using the wavelength interrogation method. Silver and gold have been used as SPR active metals followed by a high-index dielectric layer of silicon. Experimental results predict a redshift in the resonance wavelength with the increase in the refractive index of the sensing layer for a given thickness of the silicon layer. Further, as the thickness of the silicon layer increases, the sensitivity of the sensor increases. The upper limit of the silicon film thickness for the enhancement of the sensitivity has been found to be around 10 nm. The experimental results obtained on sensitivity match qualitatively with the theoretical results obtained using the N-layer model and the ray approach. The increase in sensitivity is due to the increase in the electric field intensity at the silicon-sensing-region interface. In addition to an increase in sensitivity, the silicon layer can be used to tune the resonance wavelength and can protect the metal layer from oxidation and hence can improve the durability of the probe.

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.