Resonant-enhanced localized surface plasmon resonance spectroscopy

Hybrid nanostructures of plasmonic gold nanoparticles with a-C:H thin films

Antibody binding to bovine serum albumin (BSA) and human serum albumin (HSA) immobilized onto gold nanoparticles was studied by means of localized surface plasmon resonance (LSPR) spectroscopy. Amine-modified glass was prepared by self-assembly of amine-terminated silane on substrate, and gold (Au) nanoparticles were deposited on the amine-modified glass substrate. Au nanoparticles deposited on the glass surface were functionalized by BSA and HSA. BSA immobilization was confirmed by LSPR spectroscopy in conjunction with surface-enhanced Raman scattering spectroscopy. Then, LSPR response attributable to the binding of anti-BSA and anti-HSA to BSA- and HSA-functionalized Au nanoparticles, respectively, was examined. Anti-HSA at levels larger than approximately 10 nM could be detected by HSA-immobilized chips with LSPR optical response, which was saturated at concentrations greater than approximately 650 nM of anti-HSA.

Carbohydrate immobilized on a dendrimer-coated colloidal gold surface for fabrication of a lectin-sensing device based on localized surface plasmon resonance spectroscopy

We present theoretical modeling of the local surface plasmon resonance (LSPR) induced by hollow nanoshell spheres assisted with a graphene shell, aiming to examine their potential for use as efficient narrowband absorbers in the infrared wavelength region. We investigate two designs of hollow nanoparticles; namely, a hollow graphene nanosphere with a single graphene shell, and a hollow nanosphere with double shells comprising a graphene shell wrapped around a silver shell. The electric field in each region of the nanoshell is determined by solving the Laplace equation of the potential within the electrostatic approximation (the nanoshell radius [Formula: see text]50[Formula: see text]nm). Using the calculated polarizability of nanoshells, we derive analytical expressions for the absorption and scattering cross-sections. We show that in both proposed nanocomposite models, the graphene shell affords an ultra-narrow LSPR with an absorption efficiency significantly higher than the scattering efficiency. In addition, the graphene-assisted LSPR can be tuned through the visible and infrared regions by changing the Fermi energy and thickness of the graphene layer. Another exciting finding is that the use of a silver shell in the hollow bi-shell nanoparticles provides another LSPR peak besides that induced by the graphene shell. Both LSPRs of graphene and silver shells can be overlapped by changing the optical properties of graphene and/or the geometrical parameters of the silver shell. The resulting LSPR is characterized by a dominant absorption cross-section and a significant narrowband. In both proposed nanoshell designs, the properties of LSPRs are promising for use in various optical imaging and phototherapy applications.

Optical properties of VO2 spherical nanoparticles

Surface Plasmon Resonance (SPR) and localized surface plasmon resonance (LSPR) biosensors have brought a revolutionary change to in vitro study of biological and biochemical processes due to its ability to measure extremely small changes in surface refractive index (RI), binding equilibrium and kinetics. Strategies based on LSPR have been employed to enhance the sensitivity for a variety of applications, such as diagnosis of diseases, environmental analysis, food safety, and chemical threat detection. In LSPR spectroscopy, absorption and scattering of light are greatly enhanced at frequencies that excite the LSPR, resulting in a characteristic extinction spectrum that depends on the RI of the surrounding medium. Compositional and conformational change within the surrounding medium near the sensing surface could therefore be detected as shifts in the extinction spectrum. This dissertation specifically focuses on the development and evaluation of highly sensitive LSPR biosensors for in situ study of biomolecular binding process by incorporating nanotechnology. Compared to traditional methods for biomolecular binding studies, LSPR-based biosensors offer real-time, label free detection. First, we modified the gold sensing surface of LSPR-based biosensors using nanomaterials such as gold nanoparticles (AuNPs) and polymer to enhance surface absorption and sensitivity. The performance of this type of biosensors was evaluated on the application of small heavy metal molecule binding affinity study. This biosensor exhibited ~7 fold sensitivity enhancement and binding kinetics measurement capability comparing to traditional biosensors. Second, a miniaturized cell culture system was integrated into the LSPR-based biosensor system for the purpose of real-time biomarker signaling pathway studies and drug efficacy studies with living cells. To the best of our knowledge, this is the first LSPR-based sensing platform with the capability of living cell studies. We demonstrated the living cell measurement ability by studying the VEGF signaling pathway in living SKOV-3 cells. Results have shown that the VEGF secretion level from SKOV-3 cells is 0.0137 ± 0.0012 pg per cell. Moreover, we have demonstrated bevacizumab drug regulation to the VEGF signaling pathway using this biosensor. This sensing platform could potentially help studying biomolecular binding kinetics which elucidates the underlying mechanisms of biotransportation and drug delivery.

Structure and localized surface plasmon tuning of sputtered Au nano-islands through thermal annealing

A work function (WF) centric theory is developed for the localized surface plasmon resonance (LSPR) energy (in the non-scattering regime) for ligand-capped metal nanoparticles (NPs) with atomic steps. Theoretical LSPR energy is the product of the electrochemical work function (EWF) and the attenuation factor . The semi-microscopic model for the EWF includes a curvature-dependent WF, crystallographic information through the step density (ns), partial charge of adsorption (δa), dipolar orientation, the packing density of the ligand (N0), and the number of adsorbing contacts (nL) of the capping ligand. is a function of electronic screening length (lTF) and attenuation length (led). decays exponentially with the ratio of plasmonic cloud depth (2lTF) to led. The LSPR peaks (λmax) of plasmonic metals (the same NP size) follow the reverse order of their EWF values. The LSPR absorption peak red-shifts with an increase in size (2r), ns, and N0, while blue-shifts with an increase in the number of adsorbing contacts of the capping ligand (like the citrate ion). Coinage metals, viz. Au, Ag, and Cu, exhibit size (2r < 50 nm)-dependent LSPR peaks in the visible spectrum: 420 nm ≲ λmax ≲ 520 nm, for nL = 1. Pt shows anomalous twin peaks, attributed to the distinct number of carboxylic groups of citrate capping on the metal: one for nL = 2, with size-dependent peaks in the visible spectrum: 430 nm ≲ λmax ≲ 454 nm and another for nL = 3, with peaks in the UV spectrum: 378 nm ≲ λmax ≲ 400 nm. Finally, theory shows agreement with the experimental data for citrate-capped Au and Au/Ag alloy NPs.

Plasmon properties such as peak position, extinction cross-section and local electric field intensity are strongly dependent on excited, localized surface plasmon resonance (LSPR) modes. In non-spherical copper chalcogenide nanoparticles, assignment of the LSPR peaks to the corresponding oscillation modes has been controversial and requires experimental verification. We determined the in-plane LSPR mode of roxbyite Cu7S4 nanodisks from the plasmon coupling effect of nanodisks in solution. Compared with individual Cu7S4 nanodisks, self-assembled Cu7S4 nanodisk arrays in chloroform exhibited a blue-shifted LSPR peak with weaker optical density. This strongly suggests that the singular LSPR peak in the near-infrared region mainly originates from the in-plane oscillation mode. In addition, we demonstrate that the same LSPR peak can be readily tuned by controlling the number of disks in the array.

Surface plasmon resonance of gold nanoparticle aggregates induced by halide ions

We observe using ab initio methods that localized surface plasmon resonances in icosahedral silver nanoparticles enter the asymptotic region already between diameters of 1 and 2 nm, converging close to the classical quasistatic limit around 3.4 eV. We base the observation on time-dependent density-functional theory simulations of the icosahedral silver clusters Ag$_{55}$ (1.06 nm), Ag$_{147}$ (1.60 nm), Ag$_{309}$ (2.14 nm), and Ag$_{561}$ (2.68 nm). The simulation method combines the adiabatic GLLB-SC exchange-correlation functional with real time propagation in an atomic orbital basis set using the projector-augmented wave method. The method has been implemented for the electron structure code GPAW within the scope of this work. We obtain good agreement with experimental data and modeled results, including photoemission and plasmon resonance. Moreover, we can extrapolate the ab initio results to the classical quasistatically modeled icosahedral clusters.

Development of silver/gold nanocages onto indium tin oxide glass as a reagentless plasmonic mercury sensor

Localized surface plasmon resonance (LSPR) biosensors show great potential for practical/commercial use in clinical diagnosis, home healthcare, environmental analysis, and public healthcare. However, two main issues, that is, low refractometric sensitivity and low reproducibility (large-area uniformity and batch-to-batch consistency), hinder the extensive applications of LSPR biosensors. Therefore, plasmonic nanostructures with high sensitivity and excellent reproducibility are desirable for preparing reliable LSPR sensors. Herein, we have fabricated plasmonic nanopyramid arrays (NPAs) for several batches with reproducible morphology and optical properties by elastic soft lithography and metal thermal evaporation. NPAs of various metals (i.e., Al, Au, and Ag) were also prepared by thermal evaporation with the according metals. The transmission spectra of these NPAs showed several narrow LSPR peaks in the visible-infrared wavelength region. The refractometric sensitivities of the LSPR peaks were systematically studied, and high refractometric sensitivities of 774.0, 472.8, and 421.0 nm/RIU were achieved on Al, Au, and Ag NPAs, respectively. To demonstrate the potential of the NPAs for multiplex applications, we first applied this highly sensitive Al NPA biosensor to monitoring the process of proliferation of HeLa cancer cells, in situ and in real time. Then, we demonstrated that the Au NPA was able to identify the absorbed analytes on its surface through the surface-enhanced Raman scattering spectrum. In addition, the finite difference time domain simulations were performed to reveal the electromagnetic field enhancement on NPAs. Because of the properties of high sensitivity and excellent reproducibility of the metal NPA LSPR substrates, as well as the simplicity and cost efficiency of the fabrication method, our proposed work will accelerate the practical use of LSPR sensors.

The localized surface plasmon (LSP) resonances properties of periodic arrays of nanoholes in thin gold films are investigated by using the method of discrete dipole approximation (DDA). The surface plasmon polaritons (SPPs) play important roles in amplification or suppression of the LSP resonances in the film. The LSP-SPP coupling is affirmed based on the extinction spectra calculated by the DDA. The intensity of the LSP resonances can be controlled through changing the edge-to-edge separation distances between nanoholes, the number and the diameter of the nanoholes. The calculations also indicate that the LSP resonance peak decreases with increasing the thickness of the gold film.

Botulinum neurotoxins (BoNTs), ricin, and many other biological toxins are called AB toxins possessing heterogeneous A and B subunits. We propose herein a quick and safe sensing approach to AB toxins based on their unique quaternary structures. The proposed approach utilizes IgG antibodies against their A-subunits in combination with those human cell-membrane glycolipids that act as the natural ligands of B-subunits. In practice, an IgG antibody against the A-subunit of a target toxin is selected from commercially available sources and immobilized on the surface of Au nanoparticles to constitute a multivalent IgG/Au nanoconjugate. The derived IgG/Au conjugate is used in the pretreatment process of test samples for deactivating biological toxins in the form of a ternary toxin/antibody/Au complex. This process is implemented in advance to reduce the risk of handling biological toxins in laboratory work. On the other hand, the human glycolipid is immobilized on a tiny glass plate and used as a biosensor chip. The biosensor chip is set in the chamber of a flow sensing system using localized surface plasmon resonance (LSPR) spectrometry available in portable size at relatively low cost. In principle, the LSPR sensing system enables us to perform a rapid and selective detection for different kinds of biological toxins if the human glycolipid is correctly selected and installed in the sensing system. In the present LSPR sensing approach, a target AB toxin may have been deactivated during the pretreatment process. The test sample containing the deactivated AB toxin becomes a real target to be analyzed by the sensing system. In the present, we describe the concept of employing the commercially available IgG antibody in the pretreatment process followed by a typical procedure for converting it into the multivalent antibody/Au nanoconjugate and its preliminary applications in the LSPR detection of a ricin homologue (RCA120) and BoNTs in different serotypes. The tested LSPR sensing approach has worked very well for the ricin homologue and certain serotypes of botulinum neurotoxins like BoNT/A, indicating that the prior deactivation process at their A-domains causes no significant damage to the function of their B-domains with respect to determining the host cell-membrane glycolipid. The experimental results also indicated that LSPR responses from these pretreated AB toxins are significantly amplified. That is obviously thanks to the presence of Au nanoparticles in the multivalent IgG/Au nanoconjugate. We suggest in conclusion that the proposed LSPR sensing approach will provide us with a safe and useful tool for the study of biological AB toxins based on their unique quaternary protein structures.