Surface Plasmon Resonance Studies of the Hybridization Behavior of DNA-Modified Gold Nanoparticles with Surface-Attached DNA Probes

Colloidal gold nanoparticles (AuNPs) have been extensively investigated as amplification tags to improve the sensitivity of surface plasmon resonance (SPR) biosensors. When using the so-called AuNP-enhanced SPR technique for DNA detection, the density of single-stranded DNA (ssDNA) on both the AuNPs and planar gold substrates is of crucial importance. Thus, in this work, we carried out a systematical study about the influence of surface ssDNA density onto the hybridization behavior of various DNA-modified AuNPs (DNA-AuNPs) with surface-attached DNA probes by using surface plasmon resonance spectroscopy. The lateral densities of the ssDNA on both the AuNPs and planar gold substrates were controlled by using different lengths of oligo-adenine sequence (OAS) as anchoring group. Besides SPR measurements, the amount of the captured DNA-AuNPs after the hybridization was further identified via atomic force microscope (AFM). SPR and AFM results clearly indicated that a higher ssDNA density on either the AuNPs or the gold substrates would give rise to better hybridization efficiency. Moreover, SPR data showed that the captured DNA-AuNPs could not be removed from SPR sensor surfaces using various dehybridization solutions regardless of surface ssDNA density. Consequently, it is apparent that the hybridization behavior of DNA-AuNPs was different from that of solution-phase ssDNA. Based on these data, we hypothesized that both multiple recognitions and limited accessibility might account for the hybridization of DNA-AuNPs with surface-attached ssDNA probes.

     

The Effect of Negative Curvature on the Plasmonic Coupling of Concentric Core–Shell Metallic Nanostructures

Negative curvature-dependent localized surface plasmon resonance (LSPR) properties of concentric core–shell metallic nanostructure have been studied using quasistatic approach and plasmon hybridization theory. Whether in single-layered gold nanoshell or double gold nanoshells, the oscillating surface charges always concentrate close to the poles of the metal surface with negative curvature, which results in the anisotropic local electric field distribution and affects both the inter-surface plasmonic coupling and inter-shell plasmonic coupling. Therefore, the change of the radius of the gold surface with negative curvature could modulate the plasmon hybridization and lead to the LSPR shifting. The physical mechanism of the negative curvature-dependent LSPR presents a potential for design and fabrication of nanoscale optical device based on core–shell type metallic nanostructures.     

Review of Some Interesting Surface Plasmon Resonance-enhanced Properties of Noble Metal Nanoparticles and Their Applications to Biosystems

Noble metal, especially gold (Au) and silver (Ag) nanoparticles exhibit unique and tunable optical properties on account of their surface plasmon resonance (SPR). In this review, we discuss the SPR-enhanced optical properties of noble metal nanoparticles, with an emphasis on the recent advances in the utility of these plasmonic properties in molecular-specific imaging and sensing, photo-diagnostics, and selective photothermal therapy. The strongly enhanced SPR scattering from Au nanoparticles makes them useful as bright optical tags for molecular-specific biological imaging and detection using simple dark-field optical microscopy. On the other hand, the SPR absorption of the nanoparticles has allowed their use in the selective laser photothermal therapy of cancer. We also discuss the sensitivity of the nanoparticle SPR frequency to the local medium dielectric constant, which has been successfully exploited for the optical sensing of chemical and biological analytes. Plasmon coupling between metal nanoparticle pairs is also discussed, which forms the basis for nanoparticle assembly-based biodiagnostics and the plasmon ruler for dynamic measurement of nanoscale distances in biological systems.     

Enhanced surface plasmon resonance with the modified catalytic growth of Au nanoparticles

The catalytic growth of Au nanoparticles (AuNPs) has been employed in several analytical methods for improving the detection sensitivity, or integrated with the enzyme reactions for the quantitative detection of the respective substrates. However, the catalytic growth of Au nanoparticles do not work in some situations, such as surface plasmon resonance (SPR), electrochemistry, where metal matrices were used, because metal matrices used in these techniques, e.g. Au, are susceptible to metal deposition, which increased the background seriously. In this work, a SiO(2) layer was vapor-deposited on the gold film. The inhibition of metal deposition by this SiO(2) layer was investigated by SPR sensor. The results showed that the SiO(2) layer could avoid the deposition of metal on Au film. With the low background achieved by SiO(2)-coated Au films, sensitive detection of DNA hybridization using the catalytic growth of Au nanoparticles enhanced SPR was demonstrated. The work described here maybe helpful for the development of sensitive bioanalytical methods.     

Enhanced SPR Sensitivity with Nano-Micro-Ribbon Grating—an Exhaustive Simulation Mapping

In this study, we theoretically investigate the sensing potential of 2D nano- and micro-ribbon grating structuration on the surface of Kretschmann-based surface plasmon resonance (SPR) biosensors when they are employed for detection of biomolecular binding events. Numerical simulations were carried out by employing a model based on the hybridization of two classical methods, the Fourier modal method and the finite element method. Our calculations confirm the importance of light manipulation by means of structuration of the plasmonic thin film surfaces on the nano- and micro-scales. Not only does it highlight the geometric parameters that allow the sensitivity enhancement compared with the response of the conventional SPR biosensor based on a flat surface but also describes the transition from the regime where the propagating surface plasmon mode dominates to the regime where the localized surface plasmon mode dominates. An exhaustive mapping of the biosensing potential of the 2D nano- and micro-structured biosensors surface is presented, varying the structural parameters related to the ribbon grating dimensions, i.e., the widths and thicknesses. The nano- and micro-structuration also leads to the creation of regions on biosensor chips that are characterized by strongly enhanced electromagnetic (EM) fields. New opportunities for further improving the sensitivity are offered if localization of biomolecules can be carried out in these regions of high EM fields. The continuum of nano- and micro-ribbon structured biosensors described in this study should prove a valuable tool for developing sensitive and reliable 2D-structured plasmonic biosensors.     

Experimental Study on Localized Surface Plasmon Mode Hybridization in the Near and Mid Infrared

We investigate plasmon excitations within a regular grating of double-layered gold/insulator nanoparticles in the infrared and visible spectral region. Provided a flat gold film as substrate, strong coupling between the localized surface plasmon modes and their image-like excitations in the metal is observed. The interaction results in a strong red shift of the plasmon mode as well as the splitting of the modes into levels of different angular momenta, often referred to as plasmon hybridization. The diameters of the nanoparticles are designed in a way that the splitting of the resonances occurs in the spectral region between 0.1 and 1 eV, thus being accessible using an infrared microscope. Moreover, we investigated the infrared absorption signal of gratings that contain two differently sized nanoparticles. The interaction between two autonomous localized surface plasmon excitations is investigated by analyzing their crossing behavior. In contrast to the interaction between localized surface plasmons and propagating plasmon excitations which results in pronounced anticrossing, the presented structures show no interaction between two autonomous localized surface plasmons. Finally, plasmon excitations of the nanostructured surfaces in the visible spectral region are demonstrated through photographs acquired at three different illumination angles. The change in color of the gratings demonstrates the complex interaction between propagating and localized surface plasmon modes.     

Liquid phase SPR imaging experiments for biosensors applications

Surface plasmon resonance (SPR) has recently gained attention as a label-free method for the detection of biological molecules binding onto functionalised surfaces. It is one of the most sensitive detection method for monitor variations in the thickness and refractive index in ultra-thin films. Here, the adsorption processes of oligonucleotides onto gold substrates have been investigated in aqueous buffer solution using SPR imaging measurements. The hybridization of a thiol-modified, single stranded oligonucleotide anchored to a gold surface via thiol group, with its complementary sequence has been observed and characterised monitoring the hybridization process by SPR equipment. In situ investigation of smallest changes in SPR imaging measurements dynamically performed in liquid phase in the presence of DNA complementary probes was performed. Infrared spectroscopy and scanning electron microscopy characterisation of the functionalised gold surfaces of the biosensor were compared with the images obtained by SPR experimental apparatus.     

Cellular-Like Gold Nanofeet: Synthesis, Functionalization, and Surface Enhanced Fluorescence Detection for Mercury Contaminations

The novel cellular-like gold nanofeet (CGNF) with movable gold core, which are derived from gold/silver core shell nanorods, have been generated by galvanic reaction protocol at room temperature. The optical property based on localized surface plasmon resonance (LSPR) has been evaluated in comparison with solid gold nanofeet, suggesting that obviously high LSPR sensitivity of CGNF contributes to enhancing optical effect for detection of analytes. In contrast with superquenching properties of nanogold for fluorescence detection of pollutants, highly sensitive detection of heavy metal contaminations, e.g., mercury ions, have been implemented via DNA functionalized silica-coated CGNF on the basis of surface enhanced fluorescence (SEF) approach.     

The Tunable and Well-Controlled Surface Plasmon Resonances of Au Hollow Nanostructures by a Chemical Route

Au plasmonic hollow spherical nanostructures were synthesized by electrochemical reduction (GRR, the Galvanic Replacement Reaction) using Ag nanoparticles as templates. From UV-visible absorption spectroscopy, it was found that the surface plasmon resonance (SPR) of gold hollow spherical nanostructures first showed red shift and then blue shift. However, further addition of gold precursor (HAuCl₄) resulted into a red shift of SPR peak. The morphological changes from Ag nanoparticles to Au hollow nanostructures were assessed by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX)analysis. The Mie Scattering theory based simulations of SPR of Au hollow nanostructures were performed which are in good agreement with the experimental observations. Based on the experimental observations and theoretical calculations, a complete growth mechanism for Au hollow nanostructures is proposed.     

Intracellular Localized Surface Plasmonic Sensing for Subcellular Diagnosis

This paper proposes a method for diagnosing intracellular conditions and organelles of cells with localized surface plasmonic resonance (LSPR) by directly internalizing the gold nanoparticles (AuNPs) into the cells and measuring their plasmonic properties through hyperspectral imaging. This technique will be useful for direct diagnosis of cellular organelles, which have potential for cellular biology, proteomics, pharmaceuticals, drug discovery etc. Furthermore, localization and characterization of citrate-capped gold nanoparticles in HeLa cells were studied, by hyperspectral microscopy and other imaging techniques. Here, we present the method of internalizing the gold nanoparticles into the cells and subcellular organelles to facilitate subcellular plasmonic measurements. An advanced label-free visualization technique, namely hyperspectral microscopy providing images and spectral data simultaneously, was used to confirm the internalization of gold nanoparticles and to reveal their optical properties for possible intracellular plasmonic detection. Hyperspectral technology has proved to be effective in the analysis of the spectral profile of gold nanoparticles, internalized under different conditions. Using this relatively novel technique, it is possible to study the plasmonic properties of particles, localized in different parts of the cell. The position of the plasmon bands reflects the interactions of gold nanoparticles with different subcellular systems, including particle-nucleus interactions. Our results revealed the effect of the different intracellular interactions on the aggregation pattern of gold nanoparticles, inside the cells. This novel technique opens the door to intracellular plasmonics, an entirely new field, with important potential applications in life sciences. Similarly, the characterization of AuNP inside the cell was validated using traditional methods such as light microscopy and scanning electron microscopy. Under the conditions studied in this work, gold nanoparticles were found to be non-toxic to HeLa (cervical cancer) cells.     

Novel and Sensitive Core-Shell Nanoparticles Based on Surface Plasmon Resonance

In this paper, a rough silver core-shell nanoparticle with strong electric field enhancement in the vicinity of a bumpy structure on the silver core-shell surface is reported. A dipolar plasmonic mode of the silver nanoshell is investigated by using the quasi-static approach and plasmon hybridization theory, which analytical results identify the electric field enhancement spectra in which the enhancement is optimized. As the silver shell thickness is small, the hot spots play an important role in the plasmonic field enhancement. In addition, the deposition of a rough silver shell can generate a stronger near-field enhancement near the silver surface which is more desirable than that of a smooth silver shell for sensitive detection based on SPR and surface enhanced Raman scattering (SERS). The plasmonic field enhancement of a bumpy silver core-shell nanoparticle permits the detection and characterization of bovine serum albumin (BSA) protein molecule and hemoglobin solution with a high sensitivity.     

Role of Stopband and Localized Surface Plasmon Resonance in Raman Scattering from Metallo-Dielectric Photonic Crystals

Self-assembled photonic crystals grown from different colloidal sizes are coated with gold nanoparticles preferentially on their surface. The effect of localized surface plasmon resonance and the photonic stopband on the Raman scattering from these crystals is analyzed from the angle-dependent scattering measurements. The coupling of photonic and plasmonic modes at the surface of the photonic crystal is verified by measuring the increment in Raman scattering from the crystals containing the gold nanoparticles, and this increment is found to follow the spectral trend of localized surface plasmon resonance.     

Femtomolar DNA detection by parallel colorimetric darkfield microscopy of functionalized gold nanoparticles

We introduce a sensing platform for specific detection of DNA based on the formation of gold nanoparticles dimers on a surface. The specific coupling of a second gold nanoparticle to a surface bound nanoparticle by DNA hybridization results in a red shift of the nanoparticle plasmon peak. This shift can be detected as a color change in the darkfield image of the gold nanoparticles. Parallel detection of hundreds of gold nanoparticles with a calibrated true color camera enabled us to detect specific binding of target DNA. This enables a limit of detection below 1.0×10(-14) M without the need for a spectrometer or a scanning stage.     

Plasmonic Spectral Detection of Carcinoembryonic Antigen by Preventing the Direct Binding of Rhodamine 6G with Au Nanoparticles

Carcinoembryonic antigen (CEA) was used as a separator to prevent the Rhodamine 6G (R6G)-induced aggregation of colloidal gold nanoparticles. The destroyed aggregation has been monitored by measuring the absorption and resonance light scattering peaks corresponding to the longitudinal surface plasmon resonance (SPR) of the chain-like aggregated gold nanoparticles (AuNPs). It was found that the pre-adding of CEA with different concentrations to the gold colloids before mixing them with R6G could lead to the longitudinal SPR peak decrease and blue shift. By analysing the intensity changing and wavelength shifting of the absorption spectra, CEA could be detected in a linear range from 0.2 to 4 ng/mL, and the limit of detection reaches to 0.1 ng/mL. The sensitivity of the CEA concentration dependent shifting and quenching of the plasmonic absorption and scattering corresponding to the AuNPs aggregation presents a well potential application of biologic spectral sensing.     

基于表面等离子体共振和电化学联用的DNA传感器研究进展

表面等离子共振(surface plasmon resonance,SPR)技术旨在检测物体表面附近折射率的变化,其特点是无标记、实时、灵敏和快速,该技术多用于研究分子的相互作用,包括动力学、效率常数和大分子构象变化等。电化学(electrochemical,EC)技术是一项用于定性定量研究电子转移、物质氧化还原、界面吸附等过程的成熟技术,具有简单、低成本和设备小型化的优点。现有的DNA杂交技术,例如光学、电化学或压电转导技术,主要关注于提高DNA杂交检测系统的选择性和灵敏度。传统的SPR在DNA分析方面,由于无法测量折射率的极小变化而在超灵敏检测中的应用受到限制。因此,随着纳米材料的研发和联用技术的飞速发展,SPR与EC联用的生物传感器研究越来越成为人们关注的热点。近年来,关于SPR和EC联用在DNA检测方面的综述鲜有报道。对SPR和EC检测DNA的技术原理、联用方法、应用进展等方面作出了简要的介绍,以期为表面等离子共振和电化学联用的DNA传感器相关研究提供参考。     

Controllable Mode Hybridization and Interaction Within a Plasmonic Cavity Formed by Two Bimetallic Gratings

We theoretically study mode hybridization and interaction among surface plasmon polariton Bloch wave mode, Fabry–Perot cavity mode, and waveguide mode within a plasmonic cavity composed by two parallel planar bimetallic gratings. Four hybridized modes result from mode hybridization between surface plasmon polariton Bloch wave modes on the two gratings are observed. By changing the dielectric environment, mode hybridization behavior can be manipulated. Importantly, waveguide-plasmon polariton mode due to hybridization between grating supported surface plasmon polariton Bloch wave mode and cavity supported waveguide mode is observed. We demonstrate that surface plasmon polariton Bloch wave mode and Fabry–Perot cavity mode with the same mode symmetry can interact by presenting an anticrossing behavior, which can be controlled by laterally shifting one grating with respect to the other that causes a phase difference shift of the two involving modes. The proposed plasmonic cavity offers potentials for subwavelength lithography, tunable plasmonic filter, and controllable light-matter interaction.     

Plasmonic and Energy Studies of Ag Nanoparticles in Silica-Titania Hosts

The present work reports an investigation of surface plasmon resonance (SPR) of silver nanoparticles in SiO₂–TiO₂ hosts. The surface plasmon resonance of silver nanoparticles was observed in the wavelength range 300–400 nm. Numerical calculation of SPR of silver nanoparticles with spherical morphology was done on the basis of discrete dipole approximation (DDA) method. The observed fluorescence spectrum fits well with the theoretically calculated one. The luminescence enhancement is attributed to the strong local electric field which increases the exciting and emitting photons coupled to SPR. An effort has been made to study the surface plasmon mediated excitation energy transfer (EET) between two spherical metal nanoparticles. The van der Waals (vdW) energy between plasmonic silver nanoparticles in the present hosts has been estimated.     

Gold Nanoring Arrays for Near Infrared Plasmonic Biosensing

Gold nanoring array surfaces that exhibit strong localized surface plasmon resonances (LSPR) at near infrared (NIR) wavelengths from 1.1 to 1.6 μm were used as highly sensitive real-time refractive index biosensors. Arrays of gold nanorings with tunable diameter, width, and spacing were created by the nanoscale electrodeposition of gold nanorings onto lithographically patterned nanohole array conductive surfaces over large areas (square centimeters). The bulk refractive index sensitivity of the gold nanoring arrays was determined to be up to 3,780 cm⁻¹/refractive index unit by monitoring shifts in the LSPR peak by FT-NIR transmittance spectroscopy measurements. As a first application, the surface polymerization reaction of dopamine to form polydopamine thin films on the nanoring sensor surface from aqueous solution was monitored with the real-time LSPR peak shift measurements. To demonstrate the utility of the gold nanoring arrays for LSPR biosensing, the hybridization adsorption of DNA-functionalized gold nanoparticles onto complementary DNA-functionalized gold nanoring arrays was monitored. The adsorption of DNA-modified gold nanoparticles onto nanoring arrays modified with mixed DNA monolayers that contained only 0.5 % complementary DNA was also detected; this relative surface coverage corresponds to the detection of DNA by hybridization adsorption from a 50 pM solution.

     

SPR-based DNA Detection with Metal Nanoparticles

In this short review paper, we summarize some of our ideas to utilize gold nanoparticles for the enhancement of surface plasmon resonance signals on DNA microarray. The hybridization of target-DNA capped gold nanoparticles with probe DNA on surface provides ca. ten times stronger optical contrast compared with that of target-DNA molecules. Our simulation result based on the Maxwell-Garnet theory explains well our experimental data and proves a potential of metallic nanoparticles for the substantial sensitivity enhancements for biosensor application in DNA diagnostics and bio-affinity studies, which leads to the fabrication of high resolution DNA microarrays.     

Femtomol SPR detection of DNA-PNA hybridization with the assistance of DNA-guided polyaniline deposition

The inability of surface plasmon resonance (SPR) spectroscopy to detect extremely small refractive index changes has hindered its applications in ultrasensitive DNA analysis. In this study we report a signal amplification strategy that uses DNA-templated polyaniline deposition, suitable for DNA hybridization analysis with charge neutral peptide nucleic acid (PNA) being probes. Under acidic conditions, protonated aniline monomers are adsorbed on DNA backbones through electrostatic interaction. The microenvironment provided by the DNA facilitates oxidative aniline polymerization initialized by H₂O₂ in the presence of horseradish peroxide. Under optimal conditions, the detection limit is lowered from 5 nM for conventional SPR detection to 0.1 pM. The significant sensitivity improvement is attributed to the in-situ polymer chain growth along DNA strands, which introduces drastic refractive index increases. This signal amplification approach does not involve secondary hybridization processes. The detection sensitivity obtained is much better than that of gold nanoparticle-based amplification involving a secondary hybridization process and labeled DNA detection probes.