Stimuli-responsive hydrogel-silver nanoparticles composite for development of localized surface plasmon resonance-based optical biosensor

In this paper, the development of a localized surface plasmon resonance (LSPR)-based optical enzyme biosensor using stimuli-responsive hydrogel-silver nanoparticles composite is described. This optical enzyme biosensor was constructed by immobilizing glucose oxidase (GOx) into the stimuli-responsive hydrogel. When a sample solution such as glucose was applied to the surface of this optical enzyme biosensor, the interparticle distances of the silver nanoparticles present in the stimuli-responsive hydrogel were increased, and thus the absorbance strength of the LSPR was decreased. Furthermore, hydrogen peroxide, which was produced by the enzymatic reaction, induced the degradation of highly clustered silver nanoparticles by the decomposition of hydrogen peroxide. Hence, a drastic LSPR absorbance change, which depends on the glucose concentrations, could be observed. On the basis of the abovementioned mechanism, the characterization of the LSPR-based optical enzyme biosensor was carried out. It was found that the LSPR-based optical enzyme biosensor could be used to specifically determine glucose concentrations. Furthermore, the detection limit of this biosensor was 10 pM. Therefore, this LSPR-based optical enzyme biosensor has the potential to be applied in cost-effective, highly simplified, and highly sensitive test kits for medical applications.     

Analysis of immunoreaction with localized surface plasmon resonance biosensor

The localized surface plasmon resonance (LSPR)-based optical biosensor was used as a potential tool for label-free detection of immunoreaction. The glass substrate covered with the self-assembled monolayer (SAM) of gold colloids was used widely in the sensors. Here, the glass substrate was modified by chemical hydroxylation first, and then gold colloids were immobilized on the substrate by electrostatic adsorption. The LSPR spectra were obtained on UV–vis absorption spectrometer. The specificity was examined by extensive nonspecific binding tests. The resonance condition on the local dielectric environment enables a simple form of molecular sensing. The binding of analyte to the biosensor surface causes a change in the absorbance which was responsive to the concentration of human IgG. So, the LSPR sensing yields similar results to the SPR technique, yet with much simpler instrument.     

Photometric determination of tetracycline based on surface plasmon resonance of silver nanoparticles

We report on a simple and sensitive method for the determination of tetracycline based on its reducing action on AgNO₃ in alkaline medium containing ammonia and sodium hydroxide at 65°C. As a result of this reaction, silver nanoparticles (AgNPs) are formed. The AgNPs are stabilized in solution by adding poly(vinyl pyrrolidone) as a capping agent. The formed AgNPs were identified by surface plasmon resonance absorption spectrum and transmission electron microscopy image. The plasmon absorption peak at 411 nm is proportional to the concentration of tetracycline. The calibration graph is linear in the concentration range of 0.05–5.0 mg/L with a detection limit of 0.013 mg/L. This method was applied to the determination of tetracycline in pharmaceutical products.     

Determination of dextrose in peritoneal dialysis solution by localized surface plasmon resonance technique based on silver nanoparticles formation

Determination of dextrose in peritoneal dialysis with a method based on silver nanoparticles (AgNPs) formation was investigated. In a green chemistry method, silver nanoparticles (AgNPs) were synthesized in the natural polymeric matrix of gelatin. The nanoparticles were characterized with UV–Vis spectroscopy and transmission electron microscopy (TEM). Absorbance signal of AgNPs could be applied to determine the various concentrations of dextrose solutions. Drop wise and ultrasonic methods were used and compared with each other. The dynamic range of methods with limit of detection and relative standard deviations were obtained. Results for real sample (peritoneal dialysis) were satisfied.     

A localized surface plasmon resonance light scattering-based sensing of hydroquinone via the formed silver nanoparticles in system

In this contribution, a simple strategy for the detection of hydroquinone (HQ) is proposed based on the localized surface plasmon resonance light scattering (LSPR-LS) of the silver nanoparticles (AgNPs) formed through the modified silver mirror reaction. The redox reaction between HQ and silver ammonia occurred in the coexistence of sodium hydroxide and ammonia at room temperature, where silver ammonia was reduced by HQ and resulted in the formation of AgNPs without adding the AgNPs seeds. The formed AgNPs were demonstrated to be monodisperse and uniform by transmission electron microscopy (TEM) image. We also studied the localized surface plasmon resonance absorption (LSPR-A) and LSPR-LS spectra using both a UV-vis spectrophotometer and a common spectrofluorometer, and obtained a good agreement between experiments. By carefully optimizing the amount of NaOH and ammonia of the reaction conditions, we were able to obtain the highest net intensity of LSPR-LS on the concentrations of HQ. On the basis of experimental studies, the LSPR-LS intensity enhanced linearly over the range 0.4-2.5 μmol L(-1) with the corresponding limits of determination (3σ) of 70.6 nmol L(-1). With that, the present approach was applied to detect HQ in water samples with satisfactory results.     

Studies on surface plasmon resonance and photoluminescence of silver nanoparticles

Silver nanoparticles of different sizes were prepared by citrate reduction and characterized by UV-vis absorbance spectra, TEM images and photoluminescence spectra. The morphology of the colloids obtained consists of a mixture of nanorods and spheres. The surface plasmon resonance (SPR) and photoemission properties of Ag nanoparticles are found to be sensitive to citrate concentration. A blue shift in SPR and an enhancement in photoluminescence intensity are observed with increase in citrate concentration. Effect of addition of KCl and variation of pH in photoluminescence was also studied.     

A simple and sensitive assay of gallic acid based on localized surface plasmon resonance light scattering of silver nanoparticles through modified Tollens process

A simple, low toxic, sensitive strategy based on the localized surface plasmon resonance light scattering (LSPR-LS) properties of silver nanoparticles (AgNPs) is introduced for the detection of gallic acid (GA). It was found that the silver ammonium complex, [Ag(NH(3))(2)](+)(aq), could be reduced in the alkaline medium by GA at room temperature; this reaction formed dispersed AgNPs. Transmission electron microscopy analyses were performed to ascertain the formation of AgNPs. UV-visible spectra revealed the localized surface plasmon resonance (LSPR) absorption at 410 nm corresponding to the LSPR of AgNPs. On these basis, we could quantify the GA concentration in the range of 4 × 10(-7) - 5 × 10(-6) mol L(-1) in the optimized experimental conditions. This method was used for determining the concentration of GA in artificial samples with satisfactory results. The detailed mechanism underlying this special phenomenon was elucidated.     

An optical surface plasmon resonance biosensor for determination of tetanus toxin

Surface plasmon resonance (SPR) has been successfully applied for the simple, rapid, and label-free assay of various biomolecules. This assay evaluates a novel wavelength modulation SPR biosensor for the detection of tetanus toxin. The wavelength modulation SPR biosensor is designed based on fixing the incident angle of light and measuring the reflected intensities in the resonance wavelength range spanning 400-800 nm simultaneously. Tetanus toxin (TeNT), one of the most potent toxins known, is synthesized as a 150 kDa single polypeptide chain. The SPR biosensor has been shown to be capable of directly detecting concentration of tetanus toxin as low as 0.028 Lf ml⁻¹. Under selected experimental conditions, the SPR biosensor has a good reproducibility, sensitivity and reversibility. The results illustrate how wavelength modulation SPR biosensor can be used to detect biomolecular interactions.     

Gold nanostar-enhanced surface plasmon resonance biosensor based on carboxyl-functionalized graphene oxide

A new high-sensitivity surface plasmon resonance (SPR) biosensor based on biofunctional gold nanostars (AuNSs) and carboxyl-functionalized graphene oxide (cGO) sheets was described. Compared with spherical gold nanoparticles (AuNPs), the anisotropic structure of AuNSs, which concentrates the electric charge density on its sharp tips, could enhance the local electromagnetic field and the electronic coupling effect significantly. cGO was obtained by a diazonium reaction of graphene oxide (GO) with 4-aminobenzoic acid. Compared with GO, cGO could immobilize more antibodies due to the abundant carboxylic groups on its surface. Testing results show that there are fairly large improvements in the analytical performance of the SPR biosensor using cGO/AuNSs-antigen conjugate, and the detection limit of the proposed biosensor is 0.0375 μg mL⁻¹, which is 32 times lower than that of graphene oxide-based biosensor.     

Enhancement of the sensitivity of surface plasmon resonance biosensor with colloidal gold labeling technique

In our experiment colloidal gold was used to enhance the signal obtained from the surface-plasmonresonance biosensor. Fab′ fragments of human IgG molecules were immobilized on the gold surface and reacted with the sheep-anti-human IgG(SAH-IgG) molecules in solution. It was found that when the colloidal gold labeling technique was introduced the sensitivity of surface plasmon resonance instruments increased by a factor of about 300.     

Colloidal-based localized surface plasmon resonance (LSPR) biosensor for the quantitative determination of stanozolol

This work reports the systematic preparation of biosensors through the use of functionalized glass substrates, noble metal gold colloid, and measurement by localized surface plasmon resonance (LSPR). Glass substrate was modified through chemical silanization, and the density of gold colloid was carefully controlled by optimizing the conditions of silanization through the use of mixed silanes and selective mixing procedures. At this point, samples were exposed to bioreagents and changes in the shallow dielectric constant around the particles were observed by dark-field spectroscopy. Biological binding of high affinity systems (biotin/streptavidin and antigen/antibody) was subsequently investigated by optimizing coating layers, receptor concentration profiling, and finally quantitative determination of the analyte of interest, which in this case was a small organic molecule—the widely used, synthetic anabolic steroid called stanozolol. For this system, high specificity was achieved (>97%) through extensive nonspecific binding tests, with a sensitivity measurable to a level below the minimum required performance level (MRPL) as determined by standard chromatographic methods. Analytical best-fit parameters of Hillslope and regression coefficient are also commented on for the final LSPR biosensor. The LSPR biosensor showed good reproducibility (<5% RSD) and allowed for rapid preparation of calibration curves and determination of the analyte (measurement time of each sample ca. 2 min). As an alternative method for quantitative steroidal analysis, this approach significantly simplifies the detection setup while reducing the cost of analysis. In addition the system maintains comparable sensitivity to standard surface plasmon resonance methods and offers great potential for miniaturization and development of multiplexed devices. Figure Schematic of sensor configuration indicating both min and max controls and associatedexample localized resonance curves Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A surface plasmon resonance study on the optical properties of gold nanoparticles on thin gold films

We report on an investigation of the optical properties of gold nanoparticles assembled as thin films of different thickness. The nanoparticles were linked to the surface of a gold chip by dithiol reagents and studied by surface plasmon resonance (SPR) spectroscopy and atomic force microscopy. There is good correlation between the experimental findings and theoretical simulation, and the respective data reveal the presence of ordered nanostructures in the assemblies. The shift in the SPR angle is linearly dependent on the particle size and the ratio of the different particles. SPR spectroscopy also reveals important information in terms of the optical constants of such films. This shall be further applied to in-situ quality control in the fabrication of optoelectronic, solar cell and semiconductor devices.

Attomolar sensitivity in bioassays based on surface plasmon fluorescence spectroscopy

With the aid of a dextran matrix, the metal-induced fluorescence loss of bound fluorophores can be greatly reduced, and the distance dependence of the fluorescence yield could be largely convoluted. This is optimized for the limit of detection assessment of surface plasmon fluorescence spectroscopy. The model system was designed as a direct assay with mouse IgG covalently immobilized to the carboxymethyl dextran matrix of a CM5 sensor chip from Biacore. Time-resolved ultratrace detection of fluorophore (Alexa-Fluor 647)-labeled rabbit anti-mouse antibody down to 500 aM (10-18 M) was accomplished, corresponding to a binding rate of approximately 10 molecules mm-2 min-1.     

Preparation and application of triangular silver nanoplates/chitosan composite in surface plasmon resonance biosensing

This paper reports the utilization of triangular silver nanoplates (TSNPs) to enhance the sensitivity of surface plasmon resonance (SPR) biosensor. TSNPs modified with 3-mercaptopropinic acid (MPA) were simply mixed with chitosan and glutaraldehyde to form TSNPs/chitosan composite. The composite was deposited on Au film as immobilization substrate for SPR biosensor. The novel structures of TSNPs are preserved against etching by MPA and chitosan polymer. Moreover, chitosan cross-linked by glutaraldehyde enables antibody to be immobilized on fabricated substrate directly via Schiff alkali reaction. In the optimized conditions, the resulting biosensor based on TSNPs/chitosan composite shows a satisfactory response to bovine IgG in the concentration range of 0.075–40.00 μg mL⁻¹. While the biosensor based on chitosan without TSNPs shows a response in the concentration range of 0.6–40 μg mL⁻¹ and the biosensor based on Au film shows a response in the concentration range of 2.5–40 μg mL⁻¹. The experiment results show that the sensitivity of SPR biosensor based on TSNPs/chitosan composite was significantly enhanced and the immobilization procedure of antibody was simplified.     

Cholesterol biosensor based on amino-undecanethiol self-assembled monolayer using surface plasmon resonance technique

Cholesterol oxidase has been covalently immobilized onto 11-amino-1-undecanethiol hydrochloride (AUT) self-assembled monolayer (SAM) fabricated on gold (Au) substrates using glutaraldehyde as a cross-linker. These ChOx/AUT/Au bioelectrodes characterized using contact angle (CA) measurements; electrochemical technique and atomic force microscopy (AFM) have been utilized for the estimation of cholesterol in solution using the surface plasmon resonance (SPR) technique. These biosensing electrodes exhibiting linearity from 50 to 500 mg/dL of cholesterol in solution and sensitivity of 1.23 m0/(mg dL), can be used more than 20 times and have a shelf life of about 10 weeks when stored at 4 degrees C.     

Surface plasmon resonance of silver nanoparticles on vanadium dioxide

The localized surface plasmon resonance (SPR) spectrum of silver nanoparticles fabricated on a thermochromatic film, vanadium dioxide (VO2), is studied in this paper. Owing to the temperature-dependent dielectric function of VO2, the SPR band dramatically exhibits temperature dependence in the range of 30-80 degrees C. The peak extinction wavelength, lambda(SPR), blueshifts as temperature increases and reversibly redshifts as temperature decreases. The shift magnitude (DeltalambdaSPR) is strongly dependent on the silver mass thickness, dm; a value of 50 nm of DeltalambdaSPR is achieved for particles (mean diameter 51 nm) with dm=2 nm while a value of 250 nm is achieved for particles (mean diameter 133 nm) with dm=10 nm. Beyond the SPR band, it is interesting to find that the spectral line shape of silver particles is dominated by the imaginary part of the dielectric function of VO2. These results can be interpreted based on dynamical Maxwell-Garnett theory.     

Detection of ferulic acid based on the plasmon resonance light scattering of silver nanoparticles

In this contribution, a plasmon resonance light scattering (PRLS) detection method of ferulic acid (FA) is proposed based on the formation of silver nanoparticles (NPs). It was found that, FA acted as a reducing agent in alkaline medium and could be oxidized by AgNO₃, resulting in the formation of silver NPs. The formed silver NPs, which were identified by measuring the plasmon resonance absorption spectra, PRLS spectra and transmission electron microscopy (TEM) image, display characteristic plasmon resonance optical absorption and PRLS band in the visible region. It was found that the PRLS intensity, which could be easily measured using a common spectrofluorometer, was in proportion to the concentration of FA over the range from 0.2 to 2.0 μmol l⁻¹ with the corresponding limits of determination (3σ) of 15.2 nmol l⁻¹. With that, ferulate sodium injection samples have been detected with R.S.D. lower than 3.0% and recoveries over the range of 101.2–104.5%. On the other hand, the present reaction maybe provides the basis of an environmentally friendly approach for the synthesization of silver NPs.     

Determination of trace chlorine dioxide based on the plasmon resonance scattering of silver nanoparticles

A plasmon resonance scattering (PRS) method for chlorine dioxide is reported based on the oxidization of silver nanoparticles (NPs) by it, in pH 9.1 ammonia-ammonium nitrate buffer solutions. Silver NPs exhibit strong PRS signals at 470nm, and can be oxidized by ClO(2), which results in PRS quenching at 470nm. It was found that the PRS quenching intensity is proportional to the concentration of chlorine dioxide over the range of 0.0011-0.185microg/mL, with a detection limit (3sigma) of 0.00050microg/mL and the correlation coefficient of 0.9995. The method is simple, rapid and cost effective. It was applied to the determination of chlorine dioxide in drinking water, with satisfactory results.