Assessing Plasmonic Nanoprobes in Electromagnetic Field Enhancement for SERS Detection of Biomarkers

The exploration of the plasmonic field enhancement of nanoprobes consisting of gold and magnetic core@gold shell nanoparticles has found increasing application for the development of surface-enhanced Raman spectroscopy (SERS)-based biosensors. The understanding of factors controlling the electromagnetic field enhancement, as a result of the plasmonic field enhancement of the nanoprobes in SERS biosensing applications, is critical for the design and preparation of the optimal nanoprobes. This report describes findings from theoretical calculations of the electromagnetic field intensity of dimer models of gold and magnetic core@gold shell nanoparticles in immunoassay SERS detection of biomarkers. The electromagnetic field intensities for a series of dimeric nanoprobes with antibody–antigen–antibody binding defined interparticle distances were examined in terms of nanoparticle sizes, core–shell sizes, and interparticle spacing. The results reveal that the electromagnetic field enhancement not only depended on the nanoparticle size and the relative core size and shell thicknesses of the magnetic core@shell nanoparticles but also strongly on the interparticle spacing. Some of the dependencies are also compared with experimental data from SERS detection of selected cancer biomarkers, showing good agreement. The findings have implications for the design and optimization of functional nanoprobes for SERS-based biosensors.

Influence of Spatial Dispersion on the Electromagnetic Properties of Magnetoplasmonic Nanostructures

Magnetoplasmonics based on composite nanostructures is widely used in many biomedical applications. Nanostructures, consisting of a magnetic core and a gold shell, exhibit plasmonic properties, that allow the concentration of electromagnetic energy in ultra-small volumes when used, for example, in imaging and therapy. Magnetoplasmonic nanostructures have become an indispensable tool in nanomedicine. The gold shell protects the core from oxidation and corrosion, providing a biocompatible platform for tumor imaging and cancer treatment. By adjusting the size of the core and the shell thickness, the maximum energy concentration can be shifted from the ultraviolet to the near infrared, where the depth of light penetration is maximum due to low scattering and absorption by tissues. A decrease in the thickness of the gold shell to several nanometers leads to the appearance of the quantum effect of spatial dispersion in the metal. The presence of the quantum effect can cause both a significant decrease in the level of energy concentration by plasmon particles and a shift of the maxima to the short-wavelength region, thereby reducing the expected therapeutic effect. In this study, to describe the influence of the quantum effect of spatial dispersion, we used the discrete sources method, which incorporates the generalized non-local optical response theory. This approach made it possible to account for the influence of the nonlocal effect on the optical properties of composite nanoparticles, including the impact of the asymmetry of the core-shell structure on the energy characteristics. It was found that taking spatial dispersion into account leads to a decrease in the maximum value of the concentration of electromagnetic energy up to 25%, while the blue shift can reach 15 nm.

Gold-Seeded Lithium Niobate Nanoparticles: Influence of Gold Surface Coverage on Second Harmonic Properties

Hybrid nanoparticles composed of an efficient nonlinear optical core and a gold shell can enhance and tune the nonlinear optical emission thanks to the plasmonic effect. However the influence of an incomplete gold shell, i.e., isolated gold nano-islands, is still not well studied. Here LiNbO3 (LN) core nanoparticles of 45 nm were coated with various densities of gold nano-seeds (AuSeeds). As both LN and AuSeeds bear negative surface charge, a positively-charged polymer was first coated onto LN. The number of polymer chains per LN was evaluated at 1210 by XPS and confirmed by fluorescence titration. Then, the surface coverage percentage of AuSeeds onto LN was estimated to a maximum of 30% using ICP-AES. The addition of AuSeeds was also accompanied with surface charge reversal, the negative charge increasing with the higher amount of AuSeeds. Finally, the first hyperpolarizability decreased with the increase of AuSeeds density while depolarization values for Au-seeded LN were close to the one of bare LN, showing a predominance of the second harmonic volumic contribution.

Magnetic field induced high–density SERS active assembly of Fe3O4@Au nanostar in glass capillary for food colorants detection

The Fe3O4@Au nanostar, whose anisotropic shape couples the plasmons focused on the magnetic core with the branches of gold shell, makes it hold promise for surface enhanced Raman spectroscopy (SERS)...

Design and Synthesis of Multi-Functional Superparamagnetic Core-Gold Shell Nanoparticles Coated with Chitosan and Folate for Targeted Antitumor Therapy

A dual-targeting nanomedicine composed of pH-sensitive superparamagnetic iron oxide core-gold shell SPION@Au, chitosan (CS), and folate (FA) was developed as a doxorubicin (DOX) antitumor medication. Microemulsion was used for preparation and cross-linking conjugation. The characteristics of the designed nanocomposite were studied using atomic force microscopy (AFM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction, UV-visible spectroscopy, Zeta potential and vibrating sample magnetometry (VSM), and Fourier transform infrared spectroscopy. The prepared SPION@Au-CS-DOX-FA nanoparticles (NPs) were spherical with an average diameter of 102.6 ± 7 nm and displayed an elevated drug loading behavior and sustained drug release capacity. The SPION@Au-CS-DOX-FA NPs revealed long term anti-cancer efficacy due to their cytotoxic effect and apoptotic inducing efficiency in SkBr3 cell lines. Additionally, Real-time PCR outcomes significantly showed an increase in BAK and BAX expression and a decrease in BCL-XL and BCL-2. In vivo results revealed that SPION@Au significantly decreased the tumor size in treated mice through magnetization. In conclusion, prepared SPION@Au-CS-DOX-FA could be a beneficial drug formulation for clinical breast cancer treatment.

The Effects of a Varied Gold Shell Thickness on Iron Oxide Nanoparticle Cores in Magnetic Manipulation, T1 and T2 MRI Contrasting, and Magnetic Hyperthermia

Fe3O4–Au core–shell magnetic-plasmonic nanoparticles are expected to combine both magnetic and light responsivity into a single nanosystem, facilitating combined optical and magnetic-based nanotheranostic (therapeutic and diagnostic) applications, for example, photothermal therapy in conjunction with magnetic resonance imaging (MRI) imaging. To date, the effects of a plasmonic gold shell on an iron oxide nanoparticle core in magnetic-based applications remains largely unexplored. For this study, we quantified the efficacy of magnetic iron oxide cores with various gold shell thicknesses in a number of popular magnetic-based nanotheranostic applications; these included magnetic sorting and targeting (quantifying magnetic manipulability and magnetophoresis), MRI contrasting (quantifying benchtop nuclear magnetic resonance (NMR)-based T1 and T2 relaxivity), and magnetic hyperthermia therapy (quantifying alternating magnetic-field heating). We observed a general decrease in magnetic response and efficacy with an increase of the gold shell thickness, and herein we discuss possible reasons for this reduction. The magnetophoresis speed of iron oxide nanoparticles coated with the thickest gold shell tested here (ca. 42 nm) was only ca. 1% of the non-coated bare magnetic nanoparticle, demonstrating reduced magnetic manipulability. The T1 relaxivity, r1, of the thick gold-shelled magnetic particle was ca. 22% of the purely magnetic counterpart, whereas the T2 relaxivity, r2, was 42%, indicating a reduced MRI contrasting. Lastly, the magnetic hyperthermia heating efficiency (intrinsic loss power parameter) was reduced to ca. 14% for the thickest gold shell. For all applications, the efficiency decayed exponentially with increased gold shell thickness; therefore, if the primary application of the nanostructure is magnetic-based, this work suggests that it is preferable to use a thinner gold shell or higher levels of stimuli to compensate for losses associated with the addition of the gold shell. Moreover, as thinner gold shells have better magnetic properties, have previously demonstrated superior optical properties, and are more economical than thick gold shells, it can be said that “less is more”.