Stable Localized Surface Plasmon Resonance Research Articles

Single-Particle Spectroelectrochemistry: Revealing the Electrochemical Tuning Mechanism of Chemical Interface Damping in 1,2-Benzenedithiol-Adsorbed Single Gold Nanorods.

Chemical interface damping (CID) is a newly proposed plasmon damping pathway based on interfacial hot-electron transfer from metal to adsorbate molecules. However, achieving in situ tunability of CID in single gold nanorods (AuNRs) remains a considerable challenge. Here, we present the CID effect induced by benzene 1,2-dithiol (BDT) molecule adsorption on single AuNRs and the effective electrochemical tunability of CID in BDT-adsorbed AuNRs immobilized on an indium tin oxide (ITO) surface. Manipulations of the electrochemical potential alter the electron density of AuNRs, thereby influencing and tuning the localized surface plasmon resonance (LSPR) spectrum, with cathodic potential blueshifting and anodic potential redshifting. The strong adsorption of BDT on Au induced CID in single AuNRs. The potential-induced LSPR scattering spectra of BDT-adsorbed AuNRs for linear potential sweep showed a stable LSPR spectral response, irrespective of the concentrations of BDT molecules. Due to the involvement of two Au-S bonds, BDT molecules have a higher free adsorption energy and a lower desorption rate on the Au surface. This resulted in a stable LSPR spectral response for a linear electrochemical potential sweep. Furthermore, a constant anodic and cathodic potential application showed the tunability of the CID at the BDT-Au interface.

Highly stable localized surface plasmon resonance of Cu nanoparticles obtained via oxygen plasma irradiation.

Copper nanoparticles (CuNPs) possess strong localized surface plasmon resonance (LSPR) in visible light. However, CuNPs are not chemically stable in air, which has seriously hindered the applications based on the LSPR of CuNPs. We developed an artificial method to passivate CuNPs as Al naturally does in air, preventing the oxidation of CuNPs through swift oxidation of the surface atoms via oxygen plasma irradiation. A hemispheric core-shell structure of CuNPs uniformly covered by a dense CuO shell (CuNPs@d-CuO) was constructed. The 4 nm d-CuO shell can prevent CuNPs from further oxidation. As a result, the LSPR of the CuNPs is stable in air over 180 days.

Tunable and stable localized surface plasmon resonance in SrMoO4 for enhanced visible light driven nitrogen reduction

Photocatalytic nitrogen reduction for the green synthesis of ammonia at ambient conditions has been slowed by the narrow light harvesting range, low activity and high charge recombination of photocatalysts. Plasmonic semiconducting nanomaterials are becoming the promising candidates for nitrogen photofixation because of the broad absorption spectrum, rich defects and hot carriers. In the present study, plasmonic SrMoO4 is developed by regulating the concentration of oxygen vacancies that are accompanied in the reduction process from Mo6+ to Mo5+. The stable and tunable localized surface plasmon resonance (LSPR) absorption in visible and near infrared light range makes the wide bandgap SrMoO4 utilize the solar energy more efficiently. Energetic electrons from both the intrinsic band excitation and the LSPR excitation enable the reduction of dinitrogen molecules thermodynamically in ultrapure water to ammonia. This work provides a unique clue to design efficient photocatalysts for nitrogen fixation.

Tunable and stable localized surface plasmon resonance in SrMoO4 for enhanced visible light driven nitrogen reduction

Tunable and stable localized surface plasmon resonance in SrMoO4 for enhanced visible light driven nitrogen reduction

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

This study shows development of highly sensitive and stable localized surface plasmon resonance (LSPR)-active U-bent glass and polymeric optical fiber (GOF and POF) sensor probes by a seed-mediated in situ growth technique. Here, the nickel/nickel oxide seeds (Ni/NiO, 3 to 5 nm size) were formed on the U-region of the fiber probe by sputter coating nickel under a low vacuum (3 Pa), and then, gold nanostructures (AuNSs) were grown over the Ni/NiO seeds. The evanescent wave absorbance (EWA) phenomenon in the U-bent fiber probe was exploited to monitor the growth kinetics of AuNSs in real-time. Experimental observations point to a potential galvanic replacement of Ni by Au. The newly formed AuNSs on U-bent GOF and POF probes gave rise to a LSPR-based refractive index sensitivity of 27.66 and 25.65 ΔA/ΔRIU with plasmonic peak at 600 and 570 nm, respectively. These plasmonic probes show an excellent chemical and mechanical stability, in addition to high surface enhanced Raman scattering (SERS) activity. This quick and facile technique is highly suitable for large-scale manufacture of reliable plasmonic fiber optic sensor probes for chemical and bio sensing applications.

Plasmonic active film integrating gold/silver nanostructures for H2O2 readout

A nanostructured Ag/Au adhesive film for H2O2 reagentless determination is here proposed. The film has been realised onto ELISA polystyrene microplates. Microwells surface has been initially modified with a gold nanoparticles (AuNPs)/polydopamine thin-film. The pristine AuNPs-decorated film was later functionalized with catechin (Au-CT) allowing a uniform formation of a plasmonic active nanostructured silver network in presence of Ag+. Changes in localized surface plasmon resonance (LSPR) of the silver network upon addition of H2O2 has been used as analytical signal, taking advantage of the etching phenomenon. The Ag/Au nanocomposite-film is characterized by a well-defined (LSPRmax = 405 ± 5 nm), reproducible (intraplate RSD ≤ 9.8%, n = 96; inter-plate RSD ≤ 11.4%, n = 480) and stable LSPR signal. The film's analytical features have been tested for H2O2 and glucose (bio)sensing. Satisfactory analytical performances were obtained both for H2O2 (linear range 1–200 μM, R2 = 0.9992, RSD ≤ 6.3%, LOD = 0.2 μM) and glucose (linear range 2–250 μM, R2 = 0.9998, RSD ≤ 8.9%, LOD = 0.4 μM). As proof of applicability, the determination of the two analytes in soft drinks has been carried out achieving good and reproducible recoveries (84–111%; RSD ≤ 9%). The developed nanostructured film overcomes analytical drawbacks associated with the use of colloidal dispersions in plasmonic assays carried out in solution; the low cost, robustness, ease of use and possibility of coupling enzymatic reactions appears very promising for (bio)sensors based on the detection of H2O2.

Self-Referenced Optical Fiber Sensor for Hydrogen Peroxide Detection based on LSPR of Metallic Nanoparticles in Layer-by-Layer Films.

Intensity-based optical fiber sensors are one of the most studied sensor approaches thanks to their simplicity and low cost. Nevertheless, their main issue is their lack of robustness since any light source fluctuation, or unexpected optical setup variation is directly transferred to the output signal, which, significantly reduces their reliability. In this work, a simple and robust hydrogen peroxide (H2O2) optical fiber sensor is proposed based on the Localized Surface Plasmon Resonance (LSPR) sensitivity of silver and gold metallic nanoparticles. The precise and robust detection of H2O2 concentrations in the ppm range is very interesting for the scientific community, as it is a pathological precursor in a wide variety of damage mechanisms where its presence can be used to diagnose important diseases such as Parkinson’s disease, diabetes, asthma, or even Alzheimer’s disease). In this work, the sensing principle is based the oxidation of the silver nanoparticles due the action of the hydrogen peroxide, and consequently the reduction of the efficiency of the plasmonic coupling. At the same time, gold nanoparticles show a high chemical stability, and therefore provide a stable LSPR absorption band. This provides a stable real-time reference that can be extracted from the spectral response of the optical fiber sensor, giving a reliable reading of the hydrogen peroxide concentration.

Synthesis of Copper–Silica Core–Shell Nanostructures with Sharp and Stable Localized Surface Plasmon Resonance

Copper nanoparticles exhibit intense and sharp localized surface plasmon resonance (LSPR) in the visible region; however, the LSPR peaks become weak and broad when exposed to air due to the oxidation of Cu. In this work, the Cu nanoparticles are successfully encapsulated in SiO2 by employing trioctyl-n-phosphine (TOP)-capped Cu nanoparticles for the sol–gel reaction, yielding an aqueous Cu–SiO2 core–shell suspension with stable and well-preserved LSPR properties of the Cu cores. With the TOP capping, the oxidation of the Cu cores in the microemulsion was significantly reduced, thus allowing the Cu cores to sustain the sol–gel process used for coating the SiO2 protection layer. It was found that the self-assembled TOP-capped Cu nanoparticles were spontaneously disassembled during the sol–gel reaction, thus recovering the LSPR of individual particles. During the disassembling progress, the extinction spectrum of the nanocube agglomerates evolved from a broad extinction profile to a narrow and sharp peak. Fo...

Development of Plasmon Resonance Sensing Based on Alkylthiol-Coated Triangular Silver Nanoplates on Glass Plates

In this study, we have developed localized surface plasmon resonance (LSPR) refractive index sensor systems consisting of triangular silver nanoplates (nanoprisms) immobilized on glass plates by electrostatic interactions. The nanoprisms are synthesized by exploiting light-induced morphological changes in silver nanoparticles in aqueous solution. We have demonstrated that silver nanoprisms protected with alkylthiol molecules and supported by glass plates can function as spectrally stable LSPR refractive index sensors even in ethanol solvents. The sensitivity of the nanoprisms was found to increase with decreasing carbon chain length of alkylthiol. Furthermore, we have demonstrated that nanoprisms with higher aspect ratios had higher sensitivities than those with lower aspect ratios.

Sensing using localised surface plasmon resonance sensors

The bright colours of noble metal particles have attracted considerable interest since historical times, where they were used as decorative pigments in stained glass windows. More recently, the tuneable optical properties of metal nanoparticles and their addressability via spectroscopic techniques have brought them back into the forefront of fundamental and applied research fields. Much of the recent attention concerning metal nanoparticles such as gold and silver has been their use as small-volume, ultra-sensitive label-free optical sensors. Plasmonic nanoparticles act in this case as transducers that convert changes in the local refractive index into spectral shifts of the localized surface plasmon resonance (LSPR) band. This LSPR-shift assay is a general technique for measuring binding affinities and rates from any molecule that induces a change in the local refractive index around the metallic nanostructures. By attaching molecular recognition elements (chemical or biological ligands) on the nanostructures, specificity and selectivity to the analyte of interest are introduced into the nanosensor. In this review, we will discuss the different methods used to fabricate plasmonic nanosensors. A special emphasis will be given to techniques used to link plasmonic nanostructures to surfaces. While the difference between colorimetric and refractive index sensing approaches will be briefly described, the importance to distinguish between bulk refractive index (RI) sensing and molecular near-field refractive index sensing will be discussed. The recent progress made in the development of novel surface functionalization strategies together with the formation of optically and mechanically stable LSPR sensors will be highlighted.

Stabilization of Gold Nanoparticle Films on Glass by Thermal Embedding

The poor adhesion of gold nanoparticles (NPs) to glass has been a known obstacle to studies and applications of NP-based systems, such as glass/Au-NP optical devices. Here we present a simple scheme for obtaining stable localized surface plasmon resonance (LSPR) transducers based on Au NP films immobilized on silanized glass and annealed. The procedure includes high-temperature annealing of the Au NP film, leading to partial embedding in the glass substrate and stabilization of the morphology and optical properties. The method is demonstrated using citrate-stabilized Au NPs, 20 and 63 nm mean diameter, immobilized electrostatically on glass microscope cover slides precoated with an aminosilane monolayer. Partial thermal embedding of the Au NPs in the glass occurs at temperatures in the vicinity of the glass transition temperature of the substrate. Upon annealing in air the Au NPs gradually settle into the glass and become encircled by a glass rim. In situ transmission UV-vis spectroscopy carried out during the annealing in a specially designed optical oven shows three regions: The most pronounced change of the surface plasmon (SP) band shape occurs in the first ca. 15 min of annealing; this is followed by a blue-shift of the SP band maximum (up to ca. 5 h), after which a steady red-shift of the SP band is observed (up to ca. 70 h, when the experiment was terminated). The development of the SP extinction spectrum was correlated to changes in the system structure, including thermal modification of the NP film morphology and embedding in the glass. The partially embedded Au NP films pass successfully the adhesive-tape test, while their morphology and optical response are stable toward immersion in solvents, drying, and thiol self-assembly. The enhanced adhesion is attributed to the metal NP embedding and rim formation. The stabilized NP films display a refractive index sensitivity (RIS) of 34-48 nm/RIU and 0.1-0.4 abs.u./RIU in SP band shift and extinction change, respectively. The RIS can be improved significantly by electroless deposition of Au on the embedded NPs, while the system stability is maintained. The method presented provides a simple route to obtaining stable Au NP film transducers.

Label-free optical biosensor based on localized surface plasmon resonance of immobilized gold nanorods

We describe the fabrication and characterization of a localized surface plasmon resonance (LSPR) biosensor that utilizes gold nanorods immobilized as the optical transducer which requires the intensity change at a single wavelength to be monitored as a function of receptor–analyte binding at the nanorod surface. In contrary to free gold nanorods suspended in an aqueous solution with high sensitivity to the longitudinal plasmon wavelength to the surrounding environment, the intensity of the longitudinal plasmon band based on immobilized gold nanorods is more sensitive to changes in the surrounding dielectric properties than the change in the longitudinal plasmon wavelength. Quantitative calculation gives a linear equation between the concentration ( X) of the test sample and intensity of LPB ( Y) as Y = 0.0881 + 12.9502 X and 0.1 pM anti-goat can be detected using this IgG probe in this study. This sensor chip made of immobilized gold nanorods is very stable. The immobilized gold nanorods preserved under 4 °C for 1 year yield almost the same extinction spectrum as the original nanorods. This study reveals a reliable and sensitive method to measure the intensity of longitudinal plasmon bands based on the highly stable LSPR substrate. Moreover, the performance is comparable to dynamic SPR measurements in immunoassays and can monitor the receptor–analyte reactions in real time.