Localized Surface Plasmon Resonance Transducers Research Articles

Empowering Electroless Plating to Produce Silver Nanoparticle Films for DNA Biosensing Using Localized Surface Plasmon Resonance Spectroscopy.

To facilitate the implementation of biosensors based on the localized surface plasmon resonance (LSPR) of metal nanostructures, there is a great need for cost-efficient, flexible, and tunable methods for producing plasmonic coatings. Due to its simplicity and excellent conformity, electroless plating (EP) is well suited for this task. However, it is traditionally optimized to produce continuous metal films, which cannot be employed in LSPR sensors. Here, we outline the development of an EP strategy for depositing island-like silver nanoparticle (NP) films on glass with distinct LSPR bands. The fully wet-chemical process only employs standard chemicals and proceeds within minutes at room temperature. The key step for producing spread-out NP films is an accelerated ripening of the silver seed layer in diluted hydrochloric acid, which reduces the nucleation density during plating. The reaction kinetics and mechanisms are investigated with scanning (transmission) electron microscopy (SEM/STEM), X-ray photoelectron spectroscopy (XPS), and UV-vis spectroscopy, with the latter enabling a convenient live monitoring of the deposition, allowing its termination at a stage of desired optical properties. The sensing capabilities of chemically deposited NP films as LSPR transducers are exemplified in DNA biosensing. To this end, a sensing interface is prepared using layer-by-layer (LbL) buildup of polyelectrolytes (PE), followed by adsorption and covalent immobilization of ssDNA. The obtained LSPR transducers demonstrate robustness and selectivity in sensing experiments with binding complementary and unrelated DNA strands.

Application of Surface Click Reactions to Localized Surface Plasmon Resonance (LSPR) Biosensing.

Localized surface plasmon resonance (LSPR) spectroscopy is an effective tool for sensitive, affordable, and label-free biosensing. LSPR transducers based on nanoparticulate Au films have been applied to biosensing of receptor-analyte interactions, employing primarily thiolated receptors for constructing biorecognition interfaces on nanostructured Au surfaces. This popular method suffers from a major drawback, that is, the need to prepare a thiolated receptor for each system used, which is typically synthetically complex and time-consuming. Herein, we present an alternative approach based on the click reaction between azide and terminal alkyne, which avoids the need to synthesize thiol-derivatized receptors and is applicable to the heterogeneous morphology of LSPR transducers. The receptors are tethered with an alkyne group, which is considerably simpler than thiolation, while producing a stable product. The transducer surface is modified with a layer of a commercial long-chain thiol-azide molecule, then clicked with an alkyne-dertivatized receptor to produce the biorecognition interface. This method is employed for immobilization of four different alkyne-bearing receptor molecules on Au nano-island film based LSPR transducers, followed by testing of their performance in biorecognition of specific analytes using LSPR and FTIR spectroscopies. The results establish the usefulness of click chemistry for the preparation of biorecognition interfaces on nanostructured LSPR transducers.

Stabilization of Metal Nanoparticle Films on Glass Surfaces Using Ultrathin Silica Coating

Metal nanoparticle (NP) films, prepared by adsorption of NPs from a colloidal solution onto a preconditioned solid substrate, usually form well-dispersed random NP monolayers on the surface. For certain metals (e.g., Au, Ag, Cu), the NP films display a characteristic localized surface plasmon resonance (LSPR) extinction band, conveniently measured using transmission or reflection ultraviolet-visible light (UV-vis) spectroscopy. The surface plasmon band wavelength, intensity, and shape are affected by (among other parameters) the NP spatial distribution on the surface and the effective refractive index (RI) of the surrounding medium. A major concern in the formation of such NP assemblies on surfaces is a commonly observed instability, i.e., a strong tendency of the NPs to undergo aggregation upon removal from the solution and drying, expressed as a drastic change in the LSPR band. Since various imaging modes and applications require dried NP films, preservation of the film initial (wet) morphology and optical properties upon drying are highly desirable. The latter is achieved in the present work by introducing a convenient and generally applicable method for preventing NP aggregation upon drying while preserving the original film morphology and optical response. Stabilization of Au and Ag NP monolayers toward drying is accomplished by coating the immobilized NPs with an ultrathin (3.0-3.5 nm) silica layer, deposited using a sol-gel reaction performed on an intermediate self-assembled aminosilane layer. The thin silica coating prevents NP aggregation and maintains the initial NP film morphology and LSPR response during several cycles of drying and immersion in water. It is shown that the silica-coated NP films retain their properties as effective LSPR transducers.

Oscillatory Behavior of the Long-Range Response of Localized Surface Plasmon Resonance Transducers

Localized surface plasmon resonance (LSPR) entails the resonance of light with collective charge density oscillations in nanostructured metal. The resonance wavelength and intensity are influenced by the nanostructures’ immediate environment as a result of the evanescently decaying plasmon electric field, which extends into the medium. Recent works on such systems have reported an oscillatory response of the LSPR peak wavelength and intensity at large nanostructure/adlayer separations well outside the accepted decay length of the evanescent field. This response was attributed to reflected fields, and a model based on image dipole interactions was proposed. In the present work we investigate in detail the interaction between plasmonic arrays and dielectric overlayers using both experiment and simulation. The oscillatory behavior is attributed to interference effects that modulate the energy distribution between the transmittance, reflectance, and absorbance channels. The observations are accurately modeled...

Comparative assessment of the sensitivity of localized surface plasmon resonance transducers and interference‐based Fabry‐Pérot transducers

AbstractLocalized surface plasmon resonance (LSPR) transducers have been widely investigated for use in sensing applications. An alternative approach based on interference from thin films (Fabry‐Pérot interferometers) has been previously advanced, offering a rather high sensitivity. Both methods involve easily produced substrates and simple optical setups. Here, the sensitivity offered by typical transducers of the two kinds in a usual sensing scenario is compared quantitatively, using experimental and simulated data, and their respective advantages are discussed. To facilitate the comparison a simple sensitivity parameter is proposed. It is concluded that LSPR transducers offer superior sensitivity for analytes and recognition interfaces of small dimensions (up to several nanometers), especially in a wet environment, while the interference transducers become advantageous for thicker layers in dry conditions. For LSPR transducers, significantly higher sensitivity is obtained by using reflection, rather than transmission, measurements.

Characterization of localized surface plasmon resonance transducers produced from Au25 nanoparticle multilayers

This article reports the preparation of gold plasmonic transducers using a nanoparticle self-assembly/heating method and the characterization of the films using scattering-type scanning near-field optical microscopy (s-SNOM). Nanoparticle-polymer multilayer films were prepared by the layer-by-layer assembly on glass slides by alternating exposures to monodisperse Au25 nanoparticles and ionic polymer linkers. Thermal evaporation of organic matters from the nanoparticle-polymer multilayer films at 600°C allowed the nanoparticles to coalescence and form nanostructured films. Characterization of the nanostructured films generated from Au25 nanoparticles using atomic force microscopy (AFM) showed that the films have rounded, small, island-like morphologies (d: 30–50nm) with a pit in the center of many islands. However, further characterizations with s-SNOM revealed that the produced nanoislands contain a single gold cluster in a pit surrounded by donut-shaped dielectric species. Formation of such a structure is thought to be resulted from the embedding of gold clusters under the reorganized polysiloxane binder coatings and glass surfaces during heat treatment of the Au25 nanoparticle multilayer films. The nanostructured films displayed strong surface plasmon resonance bands in UV–vis spectra with a peak absorbance occurring at ∼545–550nm. The optical sensing capability of the films was examined using d-glucose-functionalized gold island films with the interaction of Concanavalin A (ConA). The result showed that the adsorption of ConA on island films causes a large change in the LSPR band intensity.

Enantioselective analysis of melagatran via an LSPR biosensor integrated with a microfluidic chip

The impact of chiral compounds on pharmacological and biological processes is well known. With the increasing need for enantiomerically pure compounds, effective strategies for enantioseparation and chiral discrimination are in great demand. Herein we report a simple but efficient approach for the enantioselective determination of chiral compounds based on a localized surface plasmon resonance (LSPR) biosensor integrated with a microfluidic chip. A glass microfluidic chip with an effective volume of ~0.75 μL was fabricated for this application. Gold nanorods (AuNRs) with an aspect ratio of ~2.6 were self-assembled onto the surface of the inner wall of the chip to serve as LSPR transducers, which would translate the analyte binding events into quantitative concentration information. Human α-thrombin was immobilized onto the AuNR surface for enantioselective sensing of the enantiomers of melagatran. The proposed sensor was found to be highly selective for RS-melagatran, while the binding of its enantiomer, SR-melagatran, to the sensor was inactive. Under optimal conditions, the limit of detection of this sensor for RS-melagatran was found to be 0.9 nM, whereas the presence of 10,000-fold amounts of SR-melagatran did not interfere with the detection. To the best of our knowledge, this is the first demonstration of an LSPR-based enantioselective biosensor.

Optimization of Localized Surface Plasmon Resonance Transducers for Studying Carbohydrate–Protein Interactions

Noble metal nanostructures supporting localized surface plasmons (SPs) have been widely applied to chemical and biological sensing. Changes in the refractive index near the nanostructures affect the SP extinction band, making localized surface plasmon resonance (LSPR) spectroscopy a convenient tool for studying biological interactions. Carbohydrate-protein interactions are of major importance in living organisms; their study is crucial for understanding of basic biological processes and for the construction of biosensors for diagnostics and drug development. Here LSPR transducers based on gold island films prepared by evaporation on glass and annealing were optimized for monitoring the specific interaction between Concanavalin A (Con A) and D-(+)-mannose. The sugar was modified with a PEG-thiol linker and immobilized on the Au islands. Sensing assays were performed under stationary and flow conditions, the latter providing kinetic parameters for protein binding and dissociation. Ellipsometry and Fourier transform-infrared (FT-IR) data, as well as scanning electron microscopy (SEM) imaging of fixated and stained samples, furnished independent evidence for the protein-sugar recognition. Enhanced response and visual detection of protein binding was demonstrated using Au nanoparticles stabilized with the linker-modified mannose molecules. Mannose-coated transducers display an excellent selectivity toward Con A in the presence of a large excess of bovine serum albumin (BSA).

Improved Sensitivity of Localized Surface Plasmon Resonance Transducers Using Reflection Measurements.

The refractive index sensitivity (RIS) of a localized surface plasmon resonance (LSPR) transducer is one of the key parameters determining its effectiveness in sensing applications. LSPR spectra of nanoparticulate gold films, including Au island films prepared by evaporation on glass and annealing as well as immobilized Au nanoparticle (NP) films, were measured in the transmission and reflection modes. It is shown that the RIS, measured as the wavelength shift in solvents with varying refractive index (RI), is significantly higher in reflection measurements.

Sensitivity and Optimization of Localized Surface Plasmon Resonance Transducers

Gold nanoisland films displaying localized surface plasmon resonance optical response were constructed by evaporation on glass and annealing. The surface plasmon distance sensitivity and refractive index sensitivity (RIS) for island films of different nominal thicknesses and morphologies were investigated using layer-by-layer polyelectrolyte multilayer assembly. Since the polymer forms a conformal coating on the Au islands and the glass substrate between islands, the relative sensitivity of the optical response to adsorption on and between islands was evaluated. The RIS was also determined independently using a series of solvents. An apparent discrepancy between the behavior of the RIS for wavelength shift and intensity change is resolved by considering the different physical nature of the two quantities, leading to the use of a new variable, that is, RIS (for intensity change) normalized to the surface density of islands. In the present system the surface plasmon decay length and RIS are shown to be directly correlated; both parameters increase with increasing average island size. This result implies that a higher RIS is not always beneficial for sensing; maximizing the transducer optical response requires the interrelated RIS and decay length to be optimized with respect to the dimensions of the studied analyte-receptor system. It is shown that, as a rule, transducers comprising larger islands furnish better overall sensitivity for thicker adlayers, whereas thinner adlayers produce a larger response when sensed using transducers comprising smaller islands, despite the lower RIS of the latter.

Polymer-Coated Gold Island Films as Localized Plasmon Transducers for Gas Sensing

Ultrathin (typically < or = 10-nm thick) gold island films evaporated on transparent substrates show a prominent localized surface plasmon (SP) extinction in the visible-to-NIR range. Changes in the dielectric properties of the contacting medium influence the SP absorption band, providing a scheme for optical sensing based on refractive index change. In the present work, the gas sensing capability of gold island based localized surface plasmon resonance (LSPR) transducers was explored using polymeric coatings as the active interface. LSPR transducers were fabricated by spin-coating of polystyrene (PS) or polystyrene sulfonic acid, sodium salt (PSS) onto 5-nm-thick (nominal thickness) gold island films evaporated on silanized glass and annealed. Detailed characterization of the transducers was carried out using high-resolution scanning electron microscopy, cross-sectional transmission electron microscopy, and in situ atomic force microscopy under controlled atmosphere. The hydrophobic PS film exhibits swelling and significant thickness increase upon exposure to chloroform vapor and little or no change in water vapor, whereas the hydrophilic PSS film shows the opposite behavior when exposed to the same vapors. Polymer swelling upon absorption of vapors of good solvents shows a net effect of lowering the effective refractive index in the vicinity of the gold islands, manifested as a characteristic decrease of the SP band intensity and a blue shift of the band maximum. The response, measured for four different vapors, is fast (approximately 15 s) and reversible. It is shown that gold island systems coated with polymeric films can be applied to vapor recognition in an array configuration.

Biological Sensing and Interface Design in Gold Island Film Based Localized Plasmon Transducers

Discontinuous, island-type gold films (typically < or = 10 nm nominal thickness) prepared by evaporation of the metal on transparent substrates show a localized surface plasmon resonance (LSPR) extinction in the visible-to-NIR range and can be used as optical transducers for monitoring local refractive index change. Such transducers, operated in the transmission configuration, provide an effective scheme for label-free biological sensing using basic spectrophotometric equipment. Optimization of the sensitivity of LPSR transducers requires consideration of the distance between the metal island surface and the bound analyte, strongly affecting the optical response due to the fast decay of the evanescent field of localized plasmons. In the present work Au island based LSPR transducers were used to monitor antibody-antigen interactions, demonstrating the effect of the biorecognition interface thickness. Evaporated Au island films derivatized with IgG or hCG antigens were used as biological recognition elements for selective sensing of antibody binding, distinguishing between specific and nonspecific interactions. The LSPR results are supported by XPS and ellipsometry data as well as by AFM and HRSEM imaging, the latter providing actual visualization of the two protein binding steps. Increase of the recognition interface thickness leads to a concomitant decrease in the extinction and wavelength sensitivity, generally conforming to a model of an exponentially decaying surface plasmon (SP) evanescent field.